Atomic Structure

Lecture Notes

FIITJEE-DPS-MIS-DOHA, QATAR
 Lecture No-1
INTRODUCTION
The world “atom” is a Greek word meaning indivisible, i.e., an ultimate particle which cannot be further
subdivided. The idea that all matter ultimately consists of extremely small practices was conceived by
ancient Indian and Greek philosophers.
The old concept was put on firm footing by John Dalton in the form of atomic theory which he developed
in the years 1803 – 1808. This theory was a landmark in the history of chemistry. It explained successfully
a number of experimental observations such as laws of chemical combination but failed to answer the
questions such as:
 Why do the elements show different chemical activity?
 Why do the elements possess different atomic masses?
Towards the end of the nineteenth century, it began to appear that the atom itself might be composed of even
smaller particles. This change in viewpoint was brought about by experiments with electricity. Davy, in 1807
– 1808, isolated five using electricity and proposed that the elements are held together in compounds by
attractions that are electrical in nature. In 1833, Michael Faraday showed that there is a relationship between
matter and electricity. This was the first major breakthrough to suggest that the atom was not a simple
indivisible particle of all Faraday’s work, Stoney proposed that units of electrical charge are associated with
atoms. In 1891, he suggested that these units be called as electrons. Electrons is Greek word meaning amber,
a material which becomes electrically charged when rubbed with wool or silk.
The complexity of the atom was further revealed when the following discoveries were made in subsequent
years.
(i) Discovery of cathode rays.
(ii) Discovery of positive rays.
(iii) Discovery of X-rays.
(iv) Discovery of radioactivity
(v) Discovery of isotopes and isobars.
During the past 100 years, scientists have made contributions which helped in the development of modern
theory of atomic structure. The works of J.J. Thomson and Ernest Rutherford actually laid the foundation of
the modern picture of the atom. It is now believed that the atom consists of several particles called sub-atomic
particles like electron, proton, neutron, positron, neutrino, meson, etc. out of these particles, the electron, the
proton and the neutron are called fundamentals particles and are the building blocks of the atoms.

DISCOVERY OF CATHODE RAYS

Rays moved from the negative electrode to the positive electrode (Fig. 2.1). Since, the negative electrode is
referred to as cathode, these rays were called cathode rays. Further investigations were made by W. Crookes,
J. Perrin, J.J. Thomson and others.

Cathode rays possess the following properties:

(i) They travel in straight lines away from the cathode with very high velocities ranging from 109 –
1011 cm per second. A shadow of metallic object placed in the path is cast on the wall opposite
to the cathode (Fig. 2.2)

FIITJEE-DPS-MIS-DOHA, QATAR
(ii) They produce a green glow when they strike the glass wall beyond the anode. Light is emitted
when they strike the zinc sulphide screen.
(iii) They produce heat energy when they collide with the matter. It shows that cathode rays possess
kinetic energy which is converted into heat energy when stopped by matter.
(iv) They are deflected by the electric and magnetic fields. When the rays are passed between two
electrically charged plates, these are deflected towards the positively charged plate (Fig. 2.3).
they discharge a positively charged gold leaf electroscope. It shows that cathode rays carry
negative charge.

(v) The cathode rays possess kinetic energy. It is shown by the experiment that when a small pin
wheel is placed in their path, the blades of the wheel are set in motion (Fig). Thus, the cathode
rays consist of material particles which have mass and velocity. These particles carrying negative
charge were called electrons. The name “electron” was given by Stoney.

(vi) Cathode rays produce X- rays. When they fall on a material having high atomic mass, new type
of penetrating rays of very small wavelength are emitted which are called X –rays.
(vii) These rays affect the photographic plate.
(viii) These rays can penetrate through thin foils of solid materials and cause ionization in gases
through which they pass.
(ix) The nature of the cathode rays is independent of :
a. The nature of the cathode and b. The gas in the discharge tube.

FIITJEE-DPS-MIS-DOHA, QATAR
In 1897, J.J. Thomson determined the e/m value (charge/ mass) of the electron by studying the deflections
of cathode rays in electric and magnetic fields. The value of e/m has been found to be -1.7588 x 108
coulomb/g.

By performing a series of experiments. Thomson proved that whatever gas be taken in the discharge tube
and whatever be the material of the electrodes, the value of e/m is always the same. Electrons are, thus,
common universal constituents of all atoms.

Electrons are also produced by the action of ultraviolet light or X-rays on metal and from heated filaments.
β-particles emitted by radioactive materials are also electrons.
The first precise measurements of the charge on the electron was made by Robert A.Millikan in 1909 by oil
drop experiment. The apparatus used is shown in Fig.A spray of oil drops is produced by an atomizer. The
oil drops enter the apparatus through a small hole and are allowed to fall in between two

Charged plates. The space between the charged plates is irradiated by X-rays which ionize the molecules
of
air. The movements of the droplets is observed with a telescope. A droplet may absorb one or more electrons,
i.e., acquires a negative charge. By applying an electrical field on the droplet under study which balances
the downward gravitational force, the droplet becomes stationary. From the magnitude of the charge
applied on the plate and mass of droplet, the charge on the droplet was determined. The charge on the
electron was found to be -1.6022 x 10-19 coulomb. Since, an electron has the smallest charge known, it was,
thus, designated as unit negative charge
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 𝑥 10−19
m= =
𝑒/𝑚 −1.7588 𝑥 108

= 9.1096 x 10-28 g or 9.1096 x 10-31 kg

This is termed as the rest mass of the electron, i.e., mass of the electron when moving with low speed.
Mass of the electron relative to that of a hydrogen atom:

Mass of hydrogen atom

= 1.008 amu
= 1.008 x 1.66 x 10-24 g
= 1.673 x 10-24 g (since 1 amu = 1.66 x 10-24 g)

FIITJEE-DPS-MIS-DOHA, QATAR
 𝑀𝑎𝑠𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑎𝑡𝑜𝑚 1.673 𝑥 10−24
=9.1096 𝑥 10−28
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
= 1837
1
Thus, mass of an electron = 1837 x mass of hydrogen atom

1.008
= 1837
= 0.000549 amu
An electron can thus, be defined as a sub-atomic particle which carries charge – 1.60 x 10-19 coulomb, i.e.,
1
one unit negative charge and has mass 9.1 x 10-28 g, i.e., 1837 th mass of the hydrogen atom( 0.000549 amu).

DISCOVERY OF ANODE RAY OR PROTON

With the discovery of electrons, scientists started looking for positively charged particles which were
naturally expected because matter is electrically neutral under ordinary conditions. The first experiment
that led to the discovery of the positive particle was conducted by Goldstein in 1886. He used a perforated
cathode in the modified cathode ray tube(Fig).it was observed that when a high potential difference was
applied between the electrodes, not only cathode rays were produced but also a new type of rays were
produced simultaneously from anode moving towards cathode and passed through the holes or canals of
the cathode. These rays were termed canal rays since these passed through the canals of the cathode. These
were also named anode rays as these originated from anode. When the properties of these rays were studied
by Thomson, he observed that these rays consisted of positively charged particles and named them as
positive rays.
The following characteristics of the positive rays were recognized:

PROPERTIES OF ANODE RAYS

(i) The rays travel in straight lines and cast a shadow of the object placed in their path.
(ii) Like cathode rays, these rays also rotate the wheel placed in their path and also have the heating
effect. Thus, the rays possess kinetic energy, i.e., mass particles are present.
(iii) The rays produce flashes of light on zinc sulphate screen.
(iv) The rays are deflected by electric and magnetic fields in a direction opposite to that of cathode
rays. These rays are attracted towards the negatively charged plate showing thereby that these
rays carry a positive charge.
(v) These rays can pass through thin metal foils.
(vi) These rays can produce ionization in gases.
(vii) These rays are capable of producing physical and chemical changes.
(viii) Positive particles in these rays have e/m values much smaller than that of electron. This means
either m is high or the value of charge is small in comparison to electron. Since, a positive
particle is formed by the loss of an electron or electrons, the charge on the positive particle must
be an integral multiple of the charge present on the electron. Hence, for a smaller value of e/m.
it is definite that positive particles possess a high mass.

FIITJEE-DPS-MIS-DOHA, QATAR
 (ix) 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.
Accurate measurements of the charge and the mass of the particles obtained in the discharge tube
containing hydrogen, the lightest of all gases, were made by J.J. Thomson in 1906. These particles were
found to have the e/m value as +9.579 x 104 coulomb/g. this was the maximum value of e/m observed for
any positive particle. It was, thus assumed that the positive particle given by hydrogen represents a
fundamental particle of positive charge. This particle was named proton by Rutherford in 1911. Its charge
was found to be equal magnitude but opposite in sign to that of electron. Thus, proton carries a charge +
1.602 x 10-19 coulomb, i.e., one unit positive charge.

The mass of the proton, thus, can be calculated.

𝑒 1.602 𝑥 10−19
Mass of the proton = 𝑒/𝑚 = = 1.672 x 10-24 g = 1.672 x 10-27 kg
9.579 𝑥 104
1.672 𝑥 10−24
Mass of the proton in amu = 1.66𝑥 10−24 = 1.0072 amu
A proton is defined as a sub – atomic particle which has a mass nearly 1 amu ( 1.672 x10-24 g) and a charge
of +1 unit( + 1.602 x10-19 coulomb).
Protons are produced in a number of nuclear reactions. On the basis of such reactions, proton has been
recognized as a fundamentals building unit of the atom.
Dalton’s Theory of Atom

John Dalton developed his atomic theory. According to this theory the Atom is considered to be hard, dense
and smallest particle of matter, which is indivisible, the atoms belonging to a particular element, is unique.
The properties of elements differ because of the uniqueness of the atoms belonging to particular elements.
This theory provides a satisfactory basis for the laws of chemical combination. The atom can neither be
created nor be destroyed i.e., it is indestructible.

Drawbacks: It fails to explain why atoms of different kinds should differ in mass and
valency etc.

The discovery of isotopes and isobars showed that atoms of same elements may have different atomic
masses (isotopes) and atoms of different kinds may have same atomic masses (isobars).

Characteristics of the three fundamental particles are:

Electron Proton Neutron
Symbol e or e –1
P n
Approximate relative mass 1/1836 1 1
Approximate relative charge –1 +1 No charge
Mass in kg 9.109 10 –31
1.673 10 –27
1.675 10 –27
Mass in amu 5.485 10 –4 1.007 1.008
Actual charge (coulomb) 1.602 10 –19
1.602 10 –19
0
Actual charge (e.s.u.) 4.8 10 –10 4.8 10 –10 0

The neutron and proton have approximately equal masses of 1 amu and the electron is about 1836 times
lighter, its mass can sometimes be neglected as an approximation.

The electron and proton have equal, but opposite, electric charge while the neutron is not charged.

FIITJEE-DPS-MIS-DOHA, QATAR
 Lecture No-2
Models of Atom

Thomson's Model: Putting together all the facts known at that time, Thomson assumed that an atom is a
sphere of positive charges uniformly distributed, with the electrons scattered as points throughout the sphere.
This was known as plum-pudding model at that time. However this idea was dropped due to the success of -
particle scattering experiments studied by Rutherford and Mardson.

Rutherford’s Model:  -particle emitted by radioactive substance were shown to be dispositive Helium
ions (He ) having a mass of 4 units and 2 units of positive charge
Rutherford allowed a narrow beam of  -particles to fall on a very thin gold foil of thickness of the order of
4 10 –4 cm and determined the subsequent path of these particles with the help of a zinc sulphide fluorescent
screen. The zinc sulphide screen gives off a visible flash of light when struck by an   particle, as ZnS has
the remarkable property of converting kinetic energy of particle into visible light. [For this experiment,
Rutherford specifically used   particles because they are relatively heavy resulting in high momentum]

Observation
i) Majority of the  -particles pass straight through the gold strip with little or no deflection.
ii) Some -particles are deflected from their path and diverge.
iii) Very few -particles are deflected backwards through angles greater than 90°.
iv) Some were even scattered in the opposite direction at an angle of 180° [Rutherford was very much
surprised by it and remarked that "It was as incredible as if you fired a 15 inch shell at a piece of
tissue paper and it came back and hit you"].
FIITJEE-DPS-MIS-DOHA, QATAR
Conclusions
1. The fact that most of the  particles passed straight through the metal foil indicates the most part
of the atom is empty.
2. The fact that few  particles are deflected at large angles indicates the presence of a heavy
positively charged body i.e., for such large deflections to occur  -particles must have come closer
to or collided with a massive positively charged body, and he named it nucleus.
3. The fact that one in 20,000 have deflected at 180° backwards indicates that volume occupied by this
heavy positively charged body is very small in comparison to total volume of the atom.

Atomic model: On the basis of the above observation, and having realized that the rebounding  -particles
had met something even more massive than themselves inside the gold atom, Rutherford proposed an atomic
model as follows.
i) All the protons (+ve charge) and the neutrons (neutral charge) i.e. nearly the total mass of an atom
is present in a very small region at the center of the atom. The atom's central core is called nucleus.
ii) The size of the nucleus is very small in comparison to the size of the atom. Diameter of the nucleus
is about 10 –13 while the atom has a diameter of the order 10–8 of cm. So, the size of atom is 105 times
more than that of nucleus.
iii) Most of the space outside the nucleus is empty.
iv) The electrons, equal in number to the net nuclear positive charge, revolve around the nucleus with
high speed in various circular orbits.
v) The centrifugal force arising due to the high speed of an electron balances the columbic force of
attraction of the nucleus and the electron remains stable in its path. Thus according to him atom
consists of two parts (a) nucleus and (b) extra nuclear part.

Defects of Rutherford's atomic model

FIITJEE-DPS-MIS-DOHA, QATAR
1. Position of electrons: The exact positions of the electrons from the nucleus are not mentioned.

2. Stability of the atom: Neil’s Bohr pointed out that Rutherford's atom should be highly unstable.
According to the law of electro-dynamics, the electron should therefore, continuously emit radiation
and lose energy. As a result of this a moving electron will come closer and closer to the nucleus and
after passing through a spiral path, it should ultimately fall into the nucleus.

It was calculated that the electron should fall into the nucleus in less than 10–8 sec. But it is known
that electrons keep moving outside the nucleus.

To solve this problem Neil’s Bohr proposed an improved form of Rutherford's atomic model.

Before going into the details of Neil’s Bohr model we would like to introduce you some important
atomic terms.

DISCOVERY OF NEUTRON:-
The discovery of neutron was actually made about 20 years after the structure of atom was elucidated by
Rutherford. Atomic masses of different atoms could not be explained if it was accepted that atoms consisted
only of protons and electrons, thus, Rutherford ( 1920) suggested that in an atom, there must be present at
least a third type of fundamental particle which should be electrically neutral and possess mass nearly
equal to that of proton. He proposed the name for such fundamental particle as neutron. In 1932, Chadwick
bombarded beryllium with a stream of α-particles. He observed that penetrating radiations were produced
which were not affected by electric and magnetic fields. These radiations consisted of neutral particles,
which were called neutrons. The nuclear reaction can be shown as:
9
4Be + 42 He → 12 6C + 10n
Beryllium α-particle Carbon Neutron
The mass of the neutron was determined. It was 1.675 x 10-24 g, i.e., nearly equal to the mass of proton.
Thus, a neutron is a sub-atomic particle which has mass 1.675 x 10-24 g, approximately 1 amu, or nearly
equal to the mass of a proton or hydrogen atom and carries no electrical charge. The e/m value of a neutron
is thus zero.
The discovery of neutron led to slight modification of the Rutherford atomic model. The nucleus of the atom
consists of protons and neutrons. These are collectively called as nucleons. The mass of the atom is due to
total number of nucleons present in the nucleus. Neutron and proton are interconvertible in the nucleus. Its
half-life is 20 mts.

Conclusions

(i)All atoms except hydrogen atom are composed of three fundamental particles:
(a) Electron, (b) Proton, (c) Neutron.

(ii)The hydrogen atom consists of one proton and one electron and does not contain any neutron. The
properties of three fundamental particles are summarized in the following table:
(iii) All atoms are neutral in nature, i.e., total positive charge is equal to the negative charge in an atom.
The positive charge is contributed by protons and the negative charge is contributed by electrons. Every
proton and electron carries an equal and opposite charge. Thus, in an atom, Number of protons = Number
of electrons

FIITJEE-DPS-MIS-DOHA, QATAR
 ISOTOPES, ISOBARS, ISOTONES

Atoms of the same element (same atomic number, Z) having different mass numbers (atomic masses) are
termed isotopes. Out of the three fundamentals particles, neutrons are responsible for the existence of
various isotopes of an element some of the Problem s are given in the following table.

As the chemical properties of an atom depend on the number of electrons present in the atom, the isotope
of an element having same number of electrons, therefore, show similar chemical properties and occupy
the same position in the periodic table. The physical properties may be different due to different atomic
masses.
Note: Fractional atomic masses of elements are due to the presence of isotopes. For Problem , the
fractional atomic mass of chlorine (35.5) is due to the presence of 35Cl and 37Cl isotopes in the ratio of 3 :1.
𝟑 𝒙 𝟑𝟓+𝟑𝟕 𝟏𝟒𝟐
Average at. mass of chlorine = = 𝟒 = 35.5 amu
𝟒

Elements Isotopes No. of protons(z) No.of neutrons Mass number(A)

1
1𝐻 1 - 1
{ 21𝐻 (𝐷) 1 1 2
Hydrogen 3 1 2 3
1𝐻(𝑇)

16 8 8 16
8𝑂
Oxygen 8 9 17
{ 178𝑂 8 10 18
18
8𝑂
Carbon
12
6𝐶 6 6 12
13
6𝐶 6 7 13
14 6 8 14
6𝐶

Atoms which possess same atomic masses but different atomic numbers, come into existence, these atoms
are called isobars. For Problem, the value of A is fixed, i.e., 40.

*Mass number of an element is always a whole number whereas atomic mass is usually not a whole number.

FIITJEE-DPS-MIS-DOHA, QATAR
 Lecture No-3
ELECTROMAGNETIC RADIATION
Most of our information about arrangement of electrons in atoms has come from the studies of interaction of
matter with light. As to understand these interactions, it is necessary to know about the properties of
electromagnetic radiation (light).
When an object moves up and down or vibrates continuously, energy in the form of waves is transmitted by a
vibrating object to a distant place. For Problem , when a stone is thrown in a still water of a pond, a disturbance
is produced at a place where the stone strikes the water. This disturbance advances outwards in the same form
and reaches the edges of the pond. Such a disturbance is called a mechanical wave. The mechanical waves
transmit only in a material medium. Besides the mechanical waves, there are waves which do not require any
medium for their transmission. These waves are called electromagnetic waves or electromagnetic radiations.
Radio waves, infrared waves, visible light, X-rays, ultraviolet rays, gamma rays, etc., are various types of
electromagnetic radiations. Electromagnetic radiation is generated by oscillations of a charged body in a
magnetic field or of a magnet, in an electric field. These radiations or waves have electric and magnetic fields
associated with them and travel at right angles to these fields. The following are, thus, the important
characteristics of electromagnetic radiations.

 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 travelling.
 All electromagnetic radiations (waves) travel with same velocity, i.e., the velocity of light (3 x 108 ms-
1
or 3 x 1010 cm s-1).
 The electromagnetic radiations do not require any material medium for transmission. For Problem,
rays from the sun each us through space which is non- material medium.
Characteristics of Wave Motion
A wave is always characterized by the following five characteristics:
(A) Wavelength: the distance between two nearest crests or nearest troughs is called a wavelength. It is
denoted by λ (lambda) and is measured in terms of centimeter (cm) or angstrom (Å) or micrometer(μm) or
nanometer(nm).

1 Å = 10-8 cm = 10-10 m
1μm = 10-4 cm= 10-6 m
1 nm = 10-7 cm = 10-9 m
1cm = 108 Å= 104 μm=107 nm

(B) Frequency: It is defined as the number of waves which pass through a point in one second. It is denoted
by the symbol v(nu) and is measured in terms of cycles (or waves) per second (cps) or Hertz (Hz) units.
λν = distance travelled in one second = velocity = c
𝑐
Or ν=𝜆

FIITJEE-DPS-MIS-DOHA, QATAR
(C) Velocity: it is defined as the distance covered in one second by the wave. It is denoted by the letter ‘c’.
All electromagnetic waves travel with same velocity. i.e., 3 x 1010 cm/sec. λν = 3 x 1010
thus, a wave of higher frequency has a shorter wavelength while a wave of lower frequency has a longer
wavelength.
(D) Wave number: This is reciprocal of wavelength, i.e., number of wavelengths per centimeter. It is denoted
1
by the symbol 𝑣 (nu bar). 𝑣 = 𝜆 It is expressed in cm-1 or m-1
(v) Amplitude : It is defined as the height of the crest or depth of the trough of a wave. It is denoted by the
letter ‘a’. it determined the intensity of the radiation. Intensity ∝ a2
1
(vi) Time period (T): Time taken by the wave to complete one cycle or one vibration. T = 𝑣
Electromagnetic Spectrum
The arrangement of various types of electromagnetic radiations in the order of their increasing or decreasing
wavelengths or frequencies is known as electromagnetic spectrum. The wavelengths decrease in the following
order.

Low Radio High

energy waves energy
Low Television Microwaves Infrared Visible Ultraviolet X- γ- High
frequency rays rays frequency
Long waves Short
wavelength wavelength
Electromagnetic spectrum
S.No. Name Wavelength Frequency(Hz) Source
1. Radio wave 3 10 – 3 10
14 7
110 –110
5 9
Alternating current of high
frequency
2. Microwave 3 107 – 6 106 1109 – 5 1011 Klystron tube
3. Infrared (IR) 6 106 – 7600 5 1011 – 3.95 1016 Incandescent objects
4. Visible 7600–3800 3.95 1016 – 7.9 1014 Electric bulbs, sun rays
5. Ultraviolet(UV) 3800–150 7.9 1014 – 2 1016 Sun rays, arc lamps with
mercury vapours
6. X-Rays 150–0.1 2 1016 – 3 1019 Cathode rays striking metal
plate
7.  -Rays 0.1–0.01 3 1019 – 3 1020 Secondary effect of
radioactive decay
8. Cosmic Rays 0.01–zero 3 1020 –Infinity Outer space

FIITJEE-DPS-MIS-DOHA, QATAR
 Lecture No-4
QUANTUM THEORY OF RADIATION
The wave theory successfully explains many properties of electromagnetic radiations such as reflection,
refraction, diffraction, interference, polarization, etc. but fails to explain some phenomena like black body
radiation, photoelectric effect, etc.
In order to explain black body radiation and photoelectric effect, Max Planck in 1901 presented a new
theory which is known as quantum theory of radiation. It was further extended by Einstein in 1905. The
main points of the theory are:
I. A hot body emits radiant energy not continuously but discontinuously in the form of small packets
of energy called quantum (plural qunta).
II. The energy associated with each quantum is directly proportional to the frequently of radiation, i.e.,
E ∝ ν or E=hν
Where h is a constant known as Planck’s constant. Its numerical value is 6.624 x 10-27 erg-sec.
III. The energy emitted or absorbed by a body can be either one quantum or any whole number multiple
of hv, i.e., 2hv, 3hv, 4hv,…., nhv quanta of energy.

Thus,
𝑐 𝑐
Energy emitted or absorbed = nhv = nh 𝜆 (𝑣 = 𝜆)
Where n can have values 1,2,3,4 ….., etc.
The energy is, thus, quantized.
Different from of quantum energy
1 ℎ ℎ𝑐
E= hv E=hx𝑇=𝑇 E= 𝜆 E = hc𝑣̅
Limitation of electromagnetic wave theory
Electromagnetic wave theory successfully explains the properties of light such as interference, diffraction,
but it fails in explaining the following phenomena:
(i) Black body radiation
(ii) The photoelectric effect
(iii) The line spectrum of hydrogen atom
(iv) The effect of temperature on heat capacity of solids.

Black body radiation

Black body is perfect absorber and perfect emitter of the radiant energy, i.e., it can absorb and emit all
frequencies. The radiations emitted by a black body is called black body radiation.

If metal of high melting point say iron is heated it first becomes red, then yellow and white light. According
to electromagnetic wave theory, the energy is absorbed or emitted by a body continuously. Thus, energy of
electromagnetic radiation is directly proportional to intensity (Square of amplitude). However, it is
independent of the frequency and wavelength of radiation.

Thus, according to the electromagnetic wave theory, a body should emit the radiation of same wavelength
(colour) on heating at different temperature. However, the frequency of emitted radiation changes with the
temperature of the body.
At a given temperature, intensity of emitted radiation increases with decrease of wavelength and
approaches a maximum at a particular wavelength and further starts decreasing with decrease of
wavelength.

FIITJEE-DPS-MIS-DOHA, QATAR
 Explanation of black body radiation:
When a metal of high melting point is heated, its atoms (Kernals) vibrate and emit the radiation of
frequency v Frequency of emitted radiation increases, on further heating the body, the colour of emitted
radiation changes in following order:
Red → yellow → blue
⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗
𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑖𝑛𝑔 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦

Photoelectric Effect
It was observed by Hertz and Lenard around 1880 that when a clean metallic surface is irradiated by
monochromatic light of proper frequency, electrons are emitted from it.
This phenomenon of ejection of the electrons from metal surface was called as Photoelectric Effect.
It was observed that if the frequency of incident radiation is below a certain minimum value (threshold
frequency), no emission takes place however high the intensity of light may be.

Another important feature observed was that the kinetic energy of the electrons emitted is independent of
the Intensity of the light.

The kinetic energy of the electrons increases linearly with the frequency of incident light radiation. This
was highly contrary to the laws of Physics at that time i.e. the energy of the electrons should have been
proportional to the intensity of the light, not on the frequency. These features could not be properly
explained on the basis of Maxwell's concept of light i.e. light as electromagnetic wave.

According to Einstein, when a quantum of light (photon) strikes a metal surface, it imparts its energy to
the electrons in the metal. In order for an electron to escape from the surface of the metal, it must overcomes
the attractive force of the positive ions in the metal. So a part of the photon's energy is absorbed by the
metal surface to release the electron, this is known as work function of the surface and is denoted by  .
The remaining part of the energy of the photon goes into the kinetic energy of the electron emitted. If E is
the energy of the photon, KE is the kinetic energy of the electron and  be the work function of the metal
then we have;
  h0 and Ei  h
 KE  Ei –   KE  h – h0  h( – 0 )
Also, if m be the mass and v be the velocity of the electron ejected then
KE  1 2 mv2  h( – 0 ) .
Note: The electromagnetic Radiation (or wave) now emerges as an entity which shows dual nature i.e., sometimes as Wave
and sometimes as Particle (quantum aspect).

FIITJEE-DPS-MIS-DOHA, QATAR
Problem 4: In a photoelectric experiment, the collector plate is at 2.0 V with respect to emitter plate
made of copper (work function 4.5 eV). The emitter is illuminated by a source of mono-
chromatic light of wavelength 200 nm. Find the minimum and maximum kinetic energy
of photoelectrons reaching the collector.
Solution: Since plate potentials 2 V, minimum K.E. will be 2 eV. For max. K.E. use the following
relation:
Absorbed energy = Threshold energy + K.E.
c
h  4.5 1.6 10–19  K.E.

6.626 10–34  3 108
 4.5 1.6 10 –19  K.E.
200 10 –9
K.E. = 2.739 10–19 J  1.7 eV
Max K.E. = 2eV + 1.7 eV = 3.7 eV.

CLASS WORK 1:
Light of wavelength 470 nm falls on the surface of potassium meal, electrons are emitted with a
velocity 6.4 104 m / s .
(a) What is the kinetic energy of emitted electron?
(b) What is the minimum amount of energy required to remove an electron from K atom?
Ans: (a) 1.86 x 10 -21J (b) 4.18 x 10 -19J

Atomic Spectrum
The splitting of a beam of light into radiations of different wavelengths or frequencies after passing through
a prism or diffraction grating is called dispersion and the pattern of radiations observed after the dispersion
is called spectrum
Or
The spectrum is the impression produced on the screen when radiation of particular wavelengths (or
frequencies) are analyzed through a prism or a diffraction grating.

The instrument used to separate radiations of different wavelengths (or frequencies) is termed spectroscope
of spectrograph. The spectroscope consists of a prism or diffraction grating and telescope. When a
photographic film is used for recording, the instrument is called spectrograph and the film is called
spectrogram.
Depending on the source of radiations, the spectra are broadly classified into:
1. Emission spectrum and
2. Absorption spectrum
1. Emission spectrum: When light emitted by a self-luminous object is dispersed by a prism to get the
spectrum, the spectrum is called emission spectrum. It can be of the following three types.
(a) Continuous spectrum: When white light is allowed to pass through a prism, it gets resolved into several
colors. The spectrum is a rainbow of colors, i.e., violet merges into indigo, indigo into blue, blue into green
and so on. This is a continuous spectrum. i.e., there is no sharp boundary between two colors (Fig). Light
from the sun, the filament of an incandescent bulb, flame of a candle or a carbon arc can give spectrum of this
type.

FIITJEE-DPS-MIS-DOHA, QATAR
(b) Discontinuous or line spectrum: When gases of vapors of a chemical substance are heated in an electric
arc or in a Bunsen flame, light is emitted. If the ray of this is passed through a prism, a line spectrum is
produced. The lines are separated from each other by dark spaces. Each line in the spectrum corresponds
to a particular wavelength. The line spectrum is also known as atomic spectrum. The pattern of lines in the
spectra of an element is characteristic of that element and is different from the spectra of all other elements.
Therefore, the line spectrum is also regarded as the finger print of atoms of a particular element. For
Problem s, sodium vapours give two line in the yellow region of the spectrum corresponding to wavelengths
5890 Å and 5896 Å.

Note: Line spectrum can be used in chemical analysis to identify and estimate the elements present in a
sample. This technique has helped in the discovery of many elements such as rubidium, caesium, etc.
Band spectrum: It consists of distinct bright bands and is produced by an excited source in molecular state,
e.g., spectra of molecular hydrogen, CO, NH3, etc., are of this type.

Absorption spectrum: When white light having all the wavelengths of visible region is passed through a
medium and the transmitted light is dispersed by a prism, a few dark lines or bands are obtained in the
otherwise continuous spectrum. These dark lines or bands depend on the nature of absorbing media and the
spectrum is known as absorption spectrum. Like emission spectra, the absorption spectra may also be
continuous, line or band spectrum. Absorption spectrum contains less number of type of wavelengths in the
emergent light than that in incident light.

If the atom gains energy the electron passes from a lower energy level to a higher energy level, energy is
absorbed that means a specific wave length is absorbed. Consequently, a dark line will appear in the spectrum.
This dark line constitutes the absorption spectrum.

FIITJEE-DPS-MIS-DOHA, QATAR
 Lecture No-5
Bohr’s Atomic Model

Bohr developed a model for hydrogen and hydrogen like atoms one-electron species (hydrogenic species). He
applied quantum theory in considering the energy of an electron bond to the nucleus.

Important postulates:

An atom consists of a dense nucleus situated at the center with the electron revolving around it in circular
orbits without emitting any energy. The force of attraction between the nucleus and an electron is equal to
the centrifugal force of the moving electron.

Of the finite number of circular orbits possible around the nucleus, and electron can revolve only in those
orbits whose angular momentum (mvr) is an integral multiple of factor h/ 2 .

nh
mvr  where, m = mass of the electron v = velocity of the electron
2

n = orbit number in which electron is present r = radius of the orbit

As long as an electron is revolving in an orbit it neither loses nor gains energy. Hence these orbits are
called stationary states. Each stationary state is associated with a definite amount of energy and it is also
known as energy levels. The greater the distance of the energy level from the nucleus, the more is the energy
associated with it. The different energy levels are numbered as 1, 2, 3, 4, (from nucleus onwards) or K, L,
M,N etc.

Ordinarily an electron continues to move in a particular stationary state without losing energy. Such a
stable state of the atom is called as ground state or normal state.

If energy is supplied to an electron, it may jump (excite) instantaneously from lower energy (say 1) to higher
energy level (say 2, 3, 4, etc) by absorbing one quantum of energy. This new state of electron is called as
excited state. The quantum of energy absorbed is equal to the difference in energies of the two concerned
levels.

Since the excited state is less stable, atom will lose it’s energy and come back to the ground state.Energy
absorbed or released in an electron jump, (E) is given by E  E2 – E1  hv .Where E 2 and E1 are the

FIITJEE-DPS-MIS-DOHA, QATAR
energies of the electron in the first and second energy levels, and v is the frequency of radiation absorbed or
emitted.

Note: If the energy supplied to hydrogen atom is less than 13.6 eV, it will accept or absorb only those quanta which can take
it to a certain higher energy level i.e., all those photons having energy less than or more than a particular energy level
will not be absorbed by hydrogen atom. But if energy supplied to hydrogen atom is more than 13.6 eV then all photons
are absorbed and excess energy appear as kinetic energy of emitted photo electron.

Merits of Bohr’s theory

i) The experimental value of radii and energies in hydrogen atom are in good agreement with that
calculated on the basis of Bohr’s theory.
ii) Bohr’s concept of stationary state of electron explains the emission and absorption spectra of
hydrogen like atoms.
iii) The experimental values of the spectral lines of the hydrogen spectrum are in close agreement with
the calculated by Bohr’s theory.
Limitations of Bohr’s Theory
i) It does not explain the spectra of atoms or ions having more than one electron.
ii) Bohr’s atomic model failed to account for the effect of magnetic field (Zeeman effect) or electric
field (Stark effect) on the spectra of atoms or ions. It was observed that when the source of a
spectrum is placed in a strong magnetic or electric field, each spectral line further splits into a
number of lines. This observation could not be explained on the basis of Bohr’s model.
iii) de-Broglie suggested that electrons like light have dual character. It has particle and wave
character. Bohr treated the electron only as particle.
iv) Another objection to Bohr’s theory came from Heisenberg’s Uncertainty Principle. According to
this principle “it is impossible to determine simultaneously the exact position and momentum of a
small moving particle like an electron”. The postulate of Bohr, that electrons revolve in well-defined
orbits around the nucleus with well-defined velocities is thus not attainable.

Lecture No-6
Application of Bohr’s theory

Radius and Energy levels of hydrogen atom:

Consider an electron of mass `m’ and charge `e’ revolving around a nucleus of charge Ze (where, Z = atomic
number and e is the charge of the proton) with a tangential velocity v.r is the radius of the orbit in
which electron is revolving.

By Coulomb’s Law, the electrostatic force of attraction between the moving electron and nucleus is
KZe 2 1
Coulombic force  2 K (where  0 is permittivity of free space)
r 40
K  9 109 Nm 2C –2
mv 2
The centrifugal force acting on the electron is
r
Since the electrostatic force balance the centrifugal force, for the stable electron orbit.
mv 2 KZe 2
 2 … (I)
r r
KZe2
(or) v 2  … (II)
mr
According to Bohr’s postulate of angular momentum quantization, we have

FIITJEE-DPS-MIS-DOHA, QATAR
 nh
mvr 
2
nh
v
2mr
n 2h 2
v2  2 2 2 … (III)
4 m r
Equating (2) and (3)
KZe2 n 2h 2
 2 2 2
mr 4 m r
Solving for r we get
n 2h 2
r
42 mKZe2
where n = 1, 2, 3, … 

Hence only certain orbits whose radii are given by the above equation are available for the electron.
The greater the value of n, i.e., farther the level from the nucleus the greater is the radius.

The radius of the smallest orbit (n = 1) for hydrogen atom (Z = 1) is r0 .

n 2h 2 12  (6.626 10 –34 )2
r0    5.29 10 –11 m
42 me2 K 4  (3.14)2  9 10 –31  (1.6 10 –19 ) 2  9 109

ro = 0.529A0 = I Bohr
Radius of nth orbit for an atom with atomic number Z is simply written as
n2 n2
rn  r0  0.529  Å
z z

Energy level of Hydrogen atom:

The total energy, E of the electron is the sum of kinetic energy and potential energy.

Kinetic energy of the electron = 1

2 mv2
–KZe2
Potential energy 
r
Total Energy = Kinetic Energy + Potential Energy
KZe2
Total energy  1 2 mv 2 – … (IV)
r
From equation (1) we know that
mv 2 KZe 2
 2
r r
KZe2
 1 mv 2 
2
2r
Substituting this in equation (4)
KZe2 KZe 2 KZe 2
Total energy (e)  – –
2r r 2r
Substituting for r, gives us
22 mZe2 e4 K 2
E Where n = 1, 2, 3 …
n 2h 2
This expression shows that only certain energies are allowed to the electron. Since this energy
expression consists so many fundamental constant, we are giving you the following simplified
expressions.

FIITJEE-DPS-MIS-DOHA, QATAR
 Z2
E  –21.8 10 –12  erg per atom.
n2
Z2 Z2
 – 21.8 10 –19  2 J per atom = – 13.6  2 eV per atom
n n
z2
E n  –13.6 2 eV per atom
n
(1eV = 3.83 10–23 Kcal) , (1eV = 1.602 10 –12 erg), (1eV = 1.602 10 –19 J)
Z2
E  –313.6  Kcal/mole (1 cal = 4.18 J)
n2
The energies are negative since the energy of the electron in the atom is less than the energy of a free
electron (i.e., the electron is at infinite distance from the nucleus) which is taken as zero. The lowest
energy level of the atom corresponds to n = 1, and as the quantum number increases, E become less
negative.
When n =  , E = 0 which corresponds to an ionized atom i.e., the electron and nucleus are infinitely
separated. H   H  e – (Ionization).

Velocity of electron
nh nh
We know that, mvr  ;v
2 2mr
By substituting for r we are getting
2 KZe 2
v
nh
Z
Where n and z all are constant, v = 2.18 108 cm / sec.
n
Further application of Bohr’s work was made, to other one electron species (Hydrogen like Species)
such as He and Li 2 . In each case of this kind, Bohr’s prediction of the spectrum was correct.

Explanation for hydrogen spectrum by Bohr’s theory:

 According to the Bohr’s theory electron neither emits nor absorbs energy as long as it stays in a
particular orbit. However, when an atom is subjected to electric discharge or high temperature, and
electron in the atom may jump from the normal energy level, i.e., ground state to some higher energy
level i.e., exited state. Since the life time of the electron in excited state is short, it returns to the ground
state in one or more jumps.

 During each jump, energy is emitted in the form of a photon of light of definite wavelength or
frequency.

FIITJEE-DPS-MIS-DOHA, QATAR
  The frequency of the photon of light thus emitted depends upon the energy difference of the two energy
levels concerned ( n1 , n 2 ) and is given by

–22 mZe4 K 2  1 1 
hv  E 2 – E1   2 – 2
h2  n1 n 2 
2 mZ e K  1 1 
2 2 4 2
v  2 – 2
h3  n1 n 2 

 The frequencies of the spectral lines calculated with the help of above equation are found to be in good
agreement with the experimental values. Thus, Bohr’s theory elegantly explains the line spectrum of
hydrogen and hydrogen like species.

Bohr had calculated Rydberg constant from the above equation.

C 22 mZ2e4 K 2 1 1
   2 – 2
 h3  n1 n 2 
1 2 mZ e K  1 1 
2 2 4 2
  2 – 2
 h 3c  n1 n 2 
2 me K
2 4 2
Where  1.097 10 –7 m –1 or 109678 cm –1
h 3c
1 1 1
i.e. Rydberg constant (R)     RZ2  2 – 2 
  n1 n 2 
  Wave number.
Hydrogen spectrum
If an electric discharge is passed through hydrogen gas taken in a discharge tube under low pressure, and the
emitted radiation is analyzed with the help of spectrograph, it is found to consist of a series of sharp lines in
the UV, visible and IR regions. This series of lines is known as line or atomic spectrum of hydrogen. The lines
in the visible region can be directly seen on the photographic film.

Each line of the spectrum corresponds to a light of definite wavelength. The entire spectrum consists of six
series of lines each series, known after their discoverer as the Balmer, Paschen, Lyman, Brackett, Pfund and
Humphrey series. The wavelength of all these series can be expressed by a single formula.

FIITJEE-DPS-MIS-DOHA, QATAR
 1 1 1
R 2 – 2
  n1 n 2 
 = wave number
 = wave length
R = Rydberg constant (109678 cm –1 )
n1 and n 2 have integral values as follows
Series n1 n2 Main spectral lines
Lyman 1 2, 3, 4, etc Ultra-vio
Balmer 2 3, 4, 5 etc Visible
Paschen 3 4, 5, 6 etc Infra-red
Brackett 4 5, 6, 7 etc Infra-red
Pfund 5 6, 7, 8, etc Infra-red

Note: All lines in the visible region are of Ballmer series but reverse is not true, i.e., all Balmer lines will not fall
in visible region. The pattern of lines in atomic spectrum is characteristic of hydrogen.
Problem 1: Calculate the ratio of the radius of Li+2 ion in 3rd energy level to that of He+ ion in 2nd
energy level.
n2
Solution: r
z
2
r1  n1   z 2 
   
r2  n 2   z1 
n1  3 n2  2
z1  3 (for Li 2 )
z2  2 (for He )
2
r1  3   2  3
    
r2  2   3  2

CLASS WORK 2:
Calculate the radius of 3rd Bohr orbit of Be+3 ion. Ans: 1.19A0

Problem 2: How far from the nucleus is the electron in a hydrogen atom if it has energy of –0.850
eV.

Z2
Solution: En  –  21.69 10 –19
n2
Z2
–  21.69 10 –19  –0.85 1.6 10 –19
n2
n = 4 (Z = 1)
n2 16
r   0.529   0.529  8.46Å
Z 1

CLASS WORK 3:
Calculate the wavelength and energy of radiation emitted for the electronic transition from  to, n
= 1 of hydrogen atom. Ans: 9.11 x 10-8m, 2.17 x 10-18J

FIITJEE-DPS-MIS-DOHA, QATAR
Problem 3: Find the wavelengths of the first lien of He+ ion spectral series whose interval between
1 1
extreme lines is –  2.7451104 cm –1
1 2

Solution: Extreme lines means first and last.

1 1 1 1  1 1  RZ2
–  RZ2  2 – 2  – RZ
2
 2– 2

 2   n1 (n1  1)  (n1  1)
2
n
 1 
109677.76  22
2.7451104 
(n1  1)2
(n1  1)  4 n1  3
Wavelength of first line,
1 1 1
 109677.76  22   2 – 2    4689 10–8 cm  4689Å
 3 4 

CLASS WORK 4:
Show that Balmer series occurs between 3647Å and 6563Å.

Lecture No-7
Quantum Mechanical Model of Atom
The atomic model which is based on the particle and wave nature of the electron is known as wave or quantum
mechanical model of the atom. This was developed by Schrodinger in 1926. This model describes the electron
as a three-dimensional wave in the electronic field of positively charged nucleus. Schrodinger derived an
equation which describes wave motion of positively charged nucleus. Schrodinger derived an equation which
describes wave motion of an electron. The differential equation is
d 2 d 2 d 2 82 m
   2 (E – V)  0
dx 2 dy2 dz 2 h
where x, y, z are certain coordinates of the electron, m = mass of the electron, E = total energy of the electron.
V = potential energy of the electron; h = Planck's constant and  (psi)= wave function of the electron.

Significance of : The wave function may be regarded as the amplitude function expressed in terms of
coordinates x, y and z. The wave function may have positive or negative values depending upon the value of
coordinates. The main aim of Schrodinger equation is to give solution for probability approach. When the
equation is solved, it is observed that for some regions of space the value of  is negative. But the probability
must be always positive and cannot be negative, it is thus, proper to use  2 in favor of  .

Significance of 2:2 is a probability factor. It describes the probability of finding an electron within a
small space. The space in which there is maximum probability of finding an electron is termed as orbital. The
important point of the solution of the wave equation is that it provides a set of numbers called quantum
numbers which describe energies of the electron in atoms, information about the shapes and orientations of
the most probable distribution of electrons around nucleus.

FIITJEE-DPS-MIS-DOHA, QATAR
 Quantum Numbers
To understand the concept of Quantum Numbers, we must know the meaning of some terms clearly so as to
avoid any confusion.
Energy Level, Energy Shell or Orbit The non-radiating energy paths around the nucleus are called
as Energy Levels of Shells. These are specified by numbers having values 1, 2, 3, 4, ... or K, L, M, N, ... in
order of increasing energies. The energy of a particular energy level is fixed.
SUB-ENERGY LEVEL, SUB SHELL
The phenomenon of splitting of spectral lines in electric and magnetic fields reveals that there must be extra
energy levels within a definite energy level. These were called as Sub-Energy Levels or Sub-Shells.
 There are four types of sub-shells namely; s, p, d, f.
 First energy level (K or1) has one sub-shell designated as 1s,
 the second energy level (L or 2) has two sub-shell as 2s & 2p,
 the third energy level (M or 3) has three sub shell as 3s, 3p and 3d,
 the fourth energy level (N or 4) has four sub-shells as 4s, 4p, 4d and 4f.
 The energy of sub-shell increases roughly in the order: s < p < d <f.
ORBITAL
Each sub-energy level (sub-shell) is composed of one or more orbitals. These orbitals belonging to a particular
sub-shell have equal energies and are called as degenerate orbitals.
 s-sub-shell has one orbital,
 p has three orbitals,
 d have five orbitals
 f has seven orbitals.
To describe or to characterize the electrons around the nucleus in an atom, a set of four numbers is used,
called as Quantum Numbers.
These are specified such that the states available to the electrons should follows the laws of quantum
mechanics or wave mechanics.

PRINCIPAL QUANTUM NUMBER (n)

 Principal quantum number was proposed by Bohr to explain the hydrogen atomic spectrum.
 It denotes the main energy level (or shell or orbit).
 It is denoted by 'n'. It can have positive integral values from 1,2,3,4,_ _ _ (or K,L,M,N_ _
 It also describes the energy and size of the orbit. The energy and the size of orbit increases with
increase in 'n' value. Higher is the value of n, greater is its distance from the nucleus, greater is its
size and also greater is its energy.
 The maximum number of electrons that can be accommodated in a given shell is equal to 2n2.
 It gives an idea of position and energy of an electron. The energy level n = 1 corresponds to
minimum energy and subsequently n = 2, 3, 4, ..., are arranged in order of increasing energy.

AZIMUTHAL QUANTUM NUMBER (l)

 Azimuthal quantum number was proposed by Somerfield in order to explain the fine hydrogen
atomic spectrum.
 It denotes the sub-levels (or sub-shells) in the atom. It is denoted by 'l'
 The number of sub-levels in a given main energy level is equal to the principal quantum number
'n'. These sub-levels are indicated by azimuthal quantum number 'l' which can have values from 0
to n-1. For ex: In an orbit of principal quantum number n=3, there are three sublevels denoted by
l =0,1 and 2.
 Azimuthal quantum number also describes the angular momentum of electron and shape of orbitals
present in that sublevel.

FIITJEE-DPS-MIS-DOHA, QATAR
 Problem :
l = 0 (s)--- spherical
l = 1 (p)--- dumbbell
l = 2 (d)--- double dumbbell
h
The orbital Angular momentum of electron = (  1) .
2
Note that its value does not depend upon value of n.

MAGNETIC QUANTUM NUMBER (m)

 Magnetic quantum number was proposed by Lande in order to explain the Zeeman and Stark
effects. The splitting of spectral lines in strong magnetic field is called Zeeman effect and splitting
in strong electric field is called Stark effect.
 It is denoted by 'm'. It describes the orientation of orbitals.
 The number of orientations possible for orbitals in a given sublevel 'l' is equal to the (2l+1) and can
have any values from -l_ _ _ 0 _ _ _+l.
 E.g. The number of orientations (m values) possible for a sublevel l=2 is (2 x 2)+1 = 5 and the values
of m = -2,-1,0,+1 and +2.

Principal quantum number Azimuthal quantum number Magnetic quantum number

(n) (l) (m)

n=1 l=0 m=0

n=2 l = 0,1 m = -1,0,+1

n=3 l = 0,1,2 m = -2,-1,0,+1,+2

n=4 L=0,1,2,3 m=-3,-2,-1,0,+1,+2,+3

 In s- sub-shell there is only one orbital [l = 0,  m = (2l +1) = 1].
 In p sub-shell there are three orbitals corresponding to three values of m: –1, 0 +1. [l = 1  m =
(2l +1) = 3]. These three orbitals are represented as p x , p y , p z along X, Y, Z axes perpendicular to
each other.
 In d sub-shell, there are five orbitals corresponding to –2, –1, 0 +1, +2, [l = 2  m = ( 2  2  1)  5]
. These five orbitals are represented as d xy , d zx , d x2 – y2 , dz 2 .
 In f sub-shell there are seven orbitals corresponding to –3, –2, –1, 0, +1, +2, +3 [l = 3  m =
(2  3  1)  7] .
SPIN QUANTUM NUMBER (s)

 It was proposed by Goudsmit and Uhlenbeck to explain the double line structure of alkali metal
spectra.
 Spin quantum number denotes the spin of the electron on its own axis. It is denoted by 's'. It can
have only two values (+½ and -½).
 When an electron rotates around a nucleus it also spins about its axis. If the spin is clockwise, its
spin quantum number is +1/2 and is represented as  . If the spin is anti-clockwise, its value is –1/2
and is represented as  . If the value of s is +1/2, then by convention, we take that electron as the
first electron in that orbital and if the value of s is –1/2, it is taken as second electron.

FIITJEE-DPS-MIS-DOHA, QATAR
 SIGNIFICANCE OF QUANTUM NUMBERS

Quantum number Possible values Significance

1. Prinicipal quantum 1,2,3,4--- Denotes the size and energy of orbit.

number (n)

0 to n-1 Denotes the sub-level and shapes of orbitals in that

2. Azimuthal quantum
sub-level. It indicates the angular momentum of
number (l)
electron.

3. Magnetic quantum -l -0 +l Indicates the spatial orientation of orbital.

number (m)

4. Spin quantum bumber +1/2 or -1/2 Denotes the spin of electron.

(s)

Problem 5: Write down the values of quantum numbers of all the electrons present in the outermost
orbit of argon (At. No. 18)

Solution: The electronic configuration of argon is 1s 2 , 2s 2 2p6 ,3s 2 3p 2x 3p 2y 3p z2

Values of quantum numbers are:
n 1 m s
3s2 3 0 0 +1/2, –1/2
3p 2x 3 1 1 +1/2, –1/2
3p 2y 3 1 1 +1/2, –1/2
3p 2z 3 1 0 +1/2, –1/2
Problem 6: a) An electron is in 5f-orbital. What possible values of quantum numbers n, l, m and s
can it have?
b) What designation is given to an orbital having (i) n = 2, l =1, and (ii) n = 3, l = 0?

Solution: (a) For an electron in 5f-orbital, quantum number are:

1 1
n = 5, l = 3; m = –3, –2, –1, 0, +1, +2, +3 and s = either + or –
2 2
(b) (i) 2p, (ii)3s

FIITJEE-DPS-MIS-DOHA, QATAR
 AUFBAU PRINCIPLE

Aufbau is a German word meaning `building up'. This gives us a sequence in which various sub-shells are
filled up depending on the relative order of the energy of the subs-hells. The sub-shell with minimum energy
is filled up first and when this obtains maximum quota of electrons, then the next sub-shell of higher energy
starts filling.

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p.

Sub-shell N l (n+l)
1s 1 0 1
2s 2 0 2
2p 2 1 3 Lowest value of n
3s 3 0 3
3p 3 1 4 Lowest value of n
4s 4 0 4
3d 3 2 5 Lowest value of n
4p 4 1 5
5s 5 0 5
4d 4 2 6 Lowest value of n
5p 5 1 6
6s 6 0 6
4f 4 3 7 Lowest value of n
5d 5 2 7
6p 6 1 7
7s 7 0 7
5f 5 3 8 Lowest value of n
6d 6 2 8
7p 7 1 8

FIITJEE-DPS-MIS-DOHA, QATAR
Exceptions to Aufbau Principle: In some cases, it is seen that actual electronic arrangement is slightly
different from arrangement given by Aufbau principle. A simple reason behind this is that half-filled and full-
filled sub-shell have got extra stability.

Cr(24) 
 1s2 , 2s2 2p6 , 3s2 3p6 3d4 , 4s2 (Wrong)

 1s23 , 2s2 2p6 ,3s2 3p6 3d5 , 4s1 (Right)
Cu(29) 
 1s2 , 2s2 2p6 , 3s2 3p6 3d9 , 4s 2 (Wrong)

 1s2 , 2s2 2p6 , 3s2 3p6 3d10 , 4s1 (Right)

Similarly, the following elements have slightly different configurations than expected.

Nb  [Kr] 4d 4 5s1 Mo  [Kr] 4d 4 5s1 Ru 

 [Kr] 4d7 5s1
Rh  [Kr] 4d8 5s1 Pd 
 [Kr] 4d10 5s0 Ag 
 [Kr] 4d10 5s1
Pt 
 [Xe] 4f 14 5d9 6s1 Au 
 [Xe] 4f 14 5d10 6s1

Shapes of Atomic Orbitals

i) S-orbital: An electron in considered to be immersed out in the form of a cloud. The shape of the cloud
is the shape of the orbital. The cloud is not uniform but denser in the region where the probability of
finding the electron in maximum.
The orbital with the lowest energy is the 1s orbital. It is a sphere with its center of the nucleus of the
atom. The s-orbital is said to spherically symmetrical about the nucleus, so that the electronic charge
is not concentrated in any particular direction. 2s orbital is also spherically symmetrical about the
nucleus, but it is larger than (i.e., away from) the 1s orbit.
y

1s 2s
nucleus x

Z radial node

ii) p-orbitals: There are three p-orbitals: p x , p y and p z . they are dumb-bell shaped, the two levels being
separated by; a nodal plane, i.e., a plane where there is no likely hood of finding the electron. The p-
orbitals have a marked direction character, depending as whether p x , p y and p z orbital is being
considered. The p-orbitals consist of two lobes with the atomic nucleus lying between them. The axis
of each p-orbital is perpendicular to the other two. The p x , p y and p z orbitals are equivalent except for
their directional property. They have same energy; orbitals having the same energy are said to be
degenerated.

iii) d-orbitals: There are five d-orbitals. The shapes of four d-orbitals resemble four leaf cloves. The fifth
d-orbital loops different. the shapes of these orbitals are given below.

FIITJEE-DPS-MIS-DOHA, QATAR
 DUAL CHARACTER

In case of light some phenomenon like diffraction and interference can be explained on the basis of its wave
character. However, the certain other phenomenon such as black body radiation and photoelectric effect can
be explained only on the basis of its particles nature. Thus, light is said to have a dual character. Such studies
on light were made by Einstein in 1905.

Louis de-Broglie, in 1942 extended the ideal of photons to material particles such as electron and he proposed
that matter also has a dual character-as wave and as particle.
Derivation of de-Broglie equation: The wavelength of the wave associated with any material particle
was calculated by analogy with photon. In case of photon, if it is assumed to have wave character, its energy
is given by
E = h (I) (According to the Planck’s quantum theory)
Where  is the frequency of the wave and `h’ is Planck’s constant?
If the photon is supposed to have particle character, its energy is given by
E  mc 2 (II) (According to Einstein’s equation)
where `m’ is the mass of photon, `c’ is the velocity of light.
By equating (I) and (II) h  mc2 [  c/]
c
h  mc2 or,   h / mc

The above equation is applicable to material particle if the mass and velocity of photon is replaced by the
mass and velocity of material particle. Thus, for any material particle like electron.
h
  h / mv (or)  
p
Where mv = p is the momentum of the particle.

FIITJEE-DPS-MIS-DOHA, QATAR
Problem 7: 13.6 eV is needed for ionization of a hydrogen atom. An electron in a hydrogen atom in
its ground state absorbs 1.50 times as much energy as the minimum required for it to
escape from the atom. What is the wavelength of the emitted electron? ( m e = 9.109 
10–31 kg, e = 1.602  10–19 coulomb, h = 6.63  10–34 J.s)

Solution: 1.5 times of 13.6 eV i.e., 20.4 eV is absorbed by the hydrogen atom out of which 6.8 eV
(20.4 –13.6) is converted to kinetic energy. KE = 6.8 eV = 6.8 (1.602  10–19 coulomb) (1
volt) = 1.09  10 –18 J.

1
Now, KE  mv2
2
KE 2(1.09 10 –18 J
or,   2   1.55 106 m / s
m (9.109 10 kg)
–31

h (6.63 10 –34 J.s)

  
mv (9.109 10–31 kg) (1.55 106 m / s)
 4.70 10–10 metres

Problem 8: Show that de-Broglie wavelength of electrons accelerated V volt is very nearly given by
1/ 2
 150 
 (in Å =   .
 V 

h
Solution: 
2e Vm
1/ 2 1/ 2 1/ 2
 h2   (6.626 10–34 )2 1020  150  12.25
 1020  Å  –31 
  Å.
      V 
–19
 2e Vm   2 1.6 10 V 9.1 10  V
CLASS WORK 5:
Calculate the momentum of a particle which has a de-Broglie wavelength of 2.5  10–10m.
Ans: 2.64 x 10-24 KgmSce-1

Heisenberg’s Uncertainty Principle

All moving objects that we see around us e.g., a car, a ball thrown in the air etc, move along definite paths.
Hence their position and velocity can be measured accurately at any instant of time. Is it possible for subatomic
particle also?
As a consequence of dual nature of matter. Heisenberg, in 1927 gave a principle about the uncertainties in
simultaneous measurement of position and momentum (mass  velocity) of small particles. This principle
states.
“It is impossible to measure simultaneously the position and momentum of a small microscopic moving
particle with absolute accuracy or certainty i.e., if an attempt is made to measure any one of these two
quantities with higher accuracy, the other becomes less accurate”
The product of the uncertainty in position ( x) and the uncertainty in the momentum (p  m. v where m
is the mass of the particle and v is the uncertainty in velocity) is equal to or greater than h / 4 where h is
the Planck’s constant.
Thus, the mathematical expression for the Heisenberg’s uncertainty principle is simply written as
h
x.p  h / 4 or E  t 
4

FIITJEE-DPS-MIS-DOHA, QATAR
Explanation of Heisenberg’s uncertainty Principle: Suppose we attempt to measure both the
position and momentum of an electron, to pin point the position of the electron we have to use light so that
the photon of light strikes the electron and the reflected photon is seen in the microscope. As a result of the
hitting, the position as well as the velocity of the electron is distributed. The accuracy with which the
position of the particle can be measured depends upon the wavelength of the light used. The uncertainty in
position is +  . The shorter the wavelength, the greater is the accuracy. But shorter wavelength means
higher frequency and hence higher energy. This high-energy photon on striking the electron changes its
speed as well as direction. But this is not true for macroscopic moving particle. Hence Heisenberg’s
uncertainty principle is not applicable to macroscopic particles.

Problem 9: If a 1 g body is traveling along the x-axis with an uncertainty in velocity of 1 cm/s, what
is theoretical uncertainty in its position? (b) If an electron is traveling with uncertainty
in velocity of 1 m/s, what is the theoretical uncertainty in its position?

Solution: a) According the uncertainty

h
x  mv 
4
 6.628 10–27 ergs sec.
x    3 10–28 cm  3 10–30 m
4mv 4  3.14 1g 1 cms –1
6.626 10 –34 Js
b) X 
4  3.14  9.110031 kg 1 ms1
3 10–5 m  30  m
CLASS WORK 6:
In a cyclotron, the electron is accelerated by using a potential difference across the two plates. The potential
difference is measured with an accuracy of  0.150 kv. Calculate the uncertainty of position of electron
along its line of flight. Ans: 0.80 x 10-8cm
Electronic Configuration of Elements:

Quantum numbers can now characterize the electrons in an atom. To describe the arrangements and
distribution of electrons for different elements, following rules selective principles are used. The distributions
of electrons in an atom is known as the electronic configuration of that element.

Aufbau Principle:

An atom in its lowest state of energy is said to be in ground state. The ground state is the most stable in an
atom. According to Aufbau principle”

“Electrons are added progressively to the various orbitals in their order of increasing energy starting with
the orbital of lowest energy”.

The order of increasing energy may be summed up as follows

1s, 2s, 2p, 3s, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, …

As a working rule, a new electron enters an empty orbital for which the value of (n + l) is minimum. If the
value (n + l) is same for two or more orbitals, the new electron enters an orbital having lower value of n.
Pauli’s Exclusion Principle:

“No two electrons in an atom can have the same set of all the quantum numbers or one can say that no two
electrons can have the same quantized states”
Consider an electronic arrangement in 1st energy level (n = 1). For n = 1. l= 0, and m = 0. Now s can have to
values corresponding to each value of m i.e. s = +1.2, –1/2 (n, 1, possible designation of an electron in a state

FIITJEE-DPS-MIS-DOHA, QATAR
with n = 1 is 1, 0, 0, +1/2 and 1, 0, 0, –1/2 (n, l, m, s) i.e., two quantized states. This implies that an orbital
can accommodate (for n = 1, m = 0,  one orbital) maximum of two electrons having opposite spins.

The maximum number of electrons in the different subshells = 2 (2l +1).

s-sub-shell = 2, p-sub-shell = 6, d-sub-shell = 10 and f-sub-shell = 14.

Hund’s Rule of maximum Multiplicity

According to this rule: “Electrons never pair until no available empty degenerate orbitals are left to him.”

This means an electron always occupies a vacant orbital in the same sub-shell (degenerate orbital) and pairing
starts only when all of the degenerate orbitals are filled up. This means that the pairing starts with 2nd electron
in a sub-shell, 4th electron in p-sub-shell, 6th electron in d-sub-shell and 8th electron in f-sub-shell.

By doing this, the electrons stay as far away from each other as possible. This is highly reasonable if we
consider the electron-electron repulsion. Hence electrons obey Hund’s rule as it results in lower energy state
and hence more stability.

Extra Stability of Half and fully Filled Orbitals: A particularly stable system is obtained when a
set of equivalent orbitals (degenerate orbitals) is either fully filled or half filled, i.e., each containing one or a
pair of electrons. This effect is more dominant in d and f sub-shells.

This means three or six electrons in p-sub-shell, five or ten electrons in d-sub-shell, and seven or fourteen
electrons in f-sub-shell forms a stable arrangement. Note this effect when filling of electrons takes place in d
sub-shells (for atomic number Z = 24, 25, and 29, 30).
Node and Nodal Plane

Node is defined as a region where the probability of finding an electron is zero.

The planes passing through the angular nodal points are called nodal planes.
Nodes
No. of radial or spherical nodes = n – l – 1
No. of angular nodes = l, Total no. of nodes = n–1

****

FIITJEE-DPS-MIS-DOHA, QATAR