CHAPTER - 2

STRUCTURE OF ATOM
NOTES

Sub - atomic particles

Discovery of Electron
Electron was discovered by J J Thomson by Cathode ray discharge tube
experiment. A cathode ray tube is made of glass containing two thin pieces
of metal (called electrodes) sealed in it. The electrical discharge through
the gases could be observed only at very low pressures and at very high
voltages.

When a very high voltage (about 10,000 volts) is applied between

the two electrodes, no electric discharge occurs at normal pressure. When
the pressure of the gas inside the tube is less than 1 mm of mercury, a dark
space appears near the cathode. When the pressure is reduced to 0.01 mm
Hg, it fills the whole tube. When the pressure is further reduced (10-4 mm
Hg), the electric discharge passes between the electrodes and the tube
begins to glow. This is due to the striking of some invisible rays from the
cathode. These rays which start from the cathode and move away from it,
in straight lines are called cathode rays or cathode ray particles.
These rays can be further checked by making a hole in the anode and
coating the tube behind anode with phosphorescent material like zinc

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sulphide. When these rays strike the zinc sulphide coating, a bright spot on
the coating is developed
Properties of Cathode Rays
i. The cathode rays start from cathode and move towards the anode.
ii. They are invisible, but their behaviour can be observed with the help of
fluorescent or phosphorescent materials.
iii. In the absence of electrical or magnetic field, these rays travel in
straight lines.
iv. In the presence of electric or magnetic field, the cathode rays behave
similar to that of negatively charged particles. From this it is clear that the
cathode rays consist of negatively charged particles called electrons.
v. The characteristics of cathode rays (electrons) do not depend upon the
material of electrodes and the nature of the gas present in the cathode ray
tube.
vi. These rays possess kinetic energy and hence can do mechanical work.
vii. They can produce x-rays when incident on metals with high atomic
mass.
Charge to Mass Ratio of Electron
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.

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 In the absence of electric or magnetic field, the cathode rays hit the
screen at point B. When only electric field is applied, the electrons deviate
from their path and hit the cathode ray tube at point A. Similarly, when
only magnetic field is applied, electron strikes the cathode ray tube at point
C. By carefully balancing the electrical and magnetic field strength, it is
possible to bring back the electron beam to the point B. From the strength
of electric and magnetic field, Thomson was able to calculate the value of
e/me as:
e/me = 1.758 × 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).
Charge on the Electron (e)
R.A. Millikan determined the charge on the electrons by a method
known as ‘oil drop experiment’. He found that the charge on the electron
to be 1.6022 × 10–19 C.
Mass of electron (me)
The mass of the electron (me) was determined as follows:
𝑒 1.6022 × 10−19
Mass of electron (me) = =
𝑒/𝑚𝑒 1.758 ×1011
= 9.1 ×10–31 kg
Discovery of Protons
E.Goldstein modified the discharge tube experiment by perforated
(with small holes) cathode. After evacuating the tube and on applying high
voltage, he found that some rays were emitting behind the cathode and
moving in the opposite direction of cathode rays. These rays deflect to the
negative plate of electric field. So they carry positive charge and were
called anode rays or canal rays.
Properties of Canal rays
The characteristics of canal rays are:
i. They depend on the nature of gas present in the cathode ray tube. These
are positively charged gaseous ions.

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ii. The charge to mass ratio of these particles depends on the nature of the
gas.
iii. Some of the positively charged particles carry a multiple of the
fundamental unit of electric charge.
iv. The behaviour of these particles in the magnetic or electrical field is
opposite to that observed for cathode rays.
v. They can produce heating effect and can do mechanical work.
vi. They are invisible and can be observed with the help of fluorescent or
phosphorescent materials.
vii. They also travel in straight lines. The smallest and lightest positive ion
was obtained from hydrogen and was called proton.
Discovery of Neutrons
Neutrons were discovered by Chadwick by bombarding a thin sheet
of beryllium by α-particles.
4Be
9
+ 2He4 → 6C 12 + 0n 1
They are electrically neutral particles having mass slightly greater
than that of the protons.
Characteristics of sub - atomic particles

Sub atomic Symbol Discoverer Absolute Charge Relative Mass/kg

particle (in Coulomb) charge
Electron e J J Thomson -1.6022 x 10-19 -1 9.01x10-31
Proton p E.Goldstein +1.6022x10-19 +1 1.6726x10-27

Neutron n James 0 0 1.675x10-27

Chadwick

Some important terms relating to Atomic structure

Atomic Number: It is the number of protons present in the nucleus or
number of electrons present outside the nucleus.

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It is denoted by the symbol ‘Z’.
Atomic number (Z) = nuclear charge or number of protons (p)
= number of electrons (e)
Mass Number: It is the total number of protons and neutrons in atom. Or,
it is the total number of nucleons in an atom.
It is denoted by ‘A’.
i.e. Mass number (A) = no. of protons (p) + no. of neutrons (n)
or, A = p + n
By knowing the atomic number and mass number, we can calculate the
number of neutrons as: n = A – Z
If an element X has the atomic number Z and the mass number A, it is
𝐴
denoted as: 𝑍 X or ZX A
Isotopes, Isobars and Isotones
Isotopes are atoms with same atomic number but different mass
number. That is, they contain same number of protons but different
number of neutrons. Hydrogen has three isotopes: Protium (1H 1 ),
Deuterium (1H 2 or 1D 2 ) and Tritium (1H 3 or 1T 3 ). Among these,
Protium is the ordinary hydrogen and Tritium is the radioactive isotope of
Hydrogen.
The number of protons, neutrons and electrons present in the 3 types of
hydrogen are:

Isotope Number of protons Number of protons Number of neutrons

Protium 1 1 0
Deuterium 1 1 1
Tritium 1 1 2

Almost all the elements have isotopes. All the isotopes of a given
element have same chemical properties, but they differ in their physical
properties.

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 Isobars are atoms of different elements having same mass number
but different atomic number. i.e. they have different number of protons but
have equal sum of the protons and neutrons.
e.g. 6C 14 and 7N 14 18Ar
40
and 20Ca40
Isotones are atoms having same number of neutrons but have different
atomic numbers. Some examples are:

Isotones p e n
14
6C 6 6 8
15
7N 7 7 8
16
8O 8 8 8

ATOM MODELS
Thomson’s Model of Atom
J. J. Thomson proposed the first atom model, which is known as
the plum pudding or raisin pudding or watermelon model. According
to this model, an atom has a spherical shape in which the positive charge is
uniformly distributed. The electrons are distributed in it, just like the seeds
are distributed in a water melon or plums are distributed in a pudding. An
important feature of this model is that the mass of the atom is assumed to
be uniformly distributed over the atom. Also the total positive charge in an
atom is equal to the total negative charge and hence the atom is electrically
neutral.
Rutherford’s Nuclear Model of Atom
Rutherford proposed an atom model based on his α–particle scattering
experiment. He bombarded a very thin gold foil (approximately 10-7m
thickness) with α–particles.
The Experiment: A stream of high energy α–particles from a radioactive
source was directed at a thin gold foil. The thin gold foil had a circular
fluorescent zinc sulphide screen around it. Whenever α–particles struck the
screen, a tiny flash of light was produced at that point.

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Observations: The important observations made by Rutherford are:
1. Most of the α– particles passed through the gold foil without any
deviation.
2. A small fraction of the α–particles was deflected by small angles.
3. A very few α– particles (∼1 in 20,000) bounced back, that is,
were deflected by nearly 180°.
Conclusions: From the above observations, Rutherford made the
following conclusions:
1. Since most of the α–particles passed through the foil without any
deviation, most space in the atom is empty.
2. A few positively charged α– particles were deflected. This is
because the positive charge of the atom is concentrated in a very
small volume at the centre called nucleus.
3. The volume occupied by the nucleus is negligibly small as
compared to the total volume of the atom. The radius of the atom is
about 10–10 m, while that of nucleus is 10–15 m.
On the basis of above observations and conclusions, Rutherford proposed
the nuclear model (Planetary model) of atom. According to this model:
1. All the positive charge and most of the mass of the atom are
concentrated in an extremely small region called nucleus.
2. Electrons are revolving round the nucleus with a very high speed
in circular paths called orbits.

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 3. Electrons and the nucleus are held together by electrostatic forces
of attraction.
Drawbacks or Limitations of Rutherford’s atom model
1. Rutherford’s model cannot explain the stability of the atom.
2. He cannot explain the electronic structure of atom.
Wave nature of Electromagnetic Radiation
James Maxwell suggested that when electrically charged particle
moves under acceleration, alternating electrical and magnetic fields are
produced and transmitted. These fields are transmitted in the forms of
waves called electromagnetic waves or electromagnetic radiation
(emr). These are the radiations associated with electric and magnetic
fields. E.g. light.
The important characteristics of these radiations are:
1. The oscillating electric and magnetic fields are perpendicular to
each other and both are perpendicular to the direction of propagation
of the wave.
2. The electromagnetic waves do not require a medium for
propagation and can move in vacuum.
3. There are many types of electromagnetic radiations, which differ
from one another in wavelength (or frequency). These constitute
electromagnetic spectrum. The important electromagnetic radiations
in the increasing order of wavelength are: Cosmic rays, Gamma
rays, X-rays, Ultra-violet rays, Visible light, Infra red rays,
Microwaves, Radio waves.
4. All electromagnetic radiation travel through vacuum with a
constant speed of 3x108 m/s.
Some important terms relating to electromagnetic radiations
1. Frequency (ν ): It is defined as the number of waves that pass
through a given point in one second. The SI unit for frequency is
hertz (Hz, s–1).

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 2. Wavelength (λ) : It is the distance between two adjacent crusts or
two adjacent troughs. Its unit is m or cm.
3. Wave number (ῡ ): It is defined as the number of wavelengths
per unit length. It is the reciprocal of wavelength. Its unit is m–1 or
cm-1 The frequency (ν ), speed of light (c) and the wave length
(λ)are related to each other as: c = ν λ
Particle Nature of Electromagnetic Radiation: Planck’s Quantum
Theory
Some of the experimental phenomenon like diffraction and
interference can be explained by the wave nature of the electromagnetic
radiation. But some phenomena like black body radiation, photoelectric
effect, variation of heat capacity of solids with temperature, line spectra of
atoms etc. could not be explained by wave nature of emr.
Black body radiation
An ideal body which emits and absorbs all frequencies of radiations
is called a black body and the radiation emitted by such a body is called
black body radiation. The frequency distribution of radiation emitted from
a black body depends only on its temperature. At a given temperature,
intensity of radiation emitted increases with decrease of wavelength,
reaches a maximum value at a given wavelength and then starts
decreasing.
The phenomenon of black body radiation was first explained by
Max Planck by his Quantum theory. According to this theory:
1. Atoms and molecules could emit (or absorb) energy not in a continuous
manner, but discontinuously in small packets of energy called quanta or
photons.
2. The energy (E ) of a quantum of radiation is proportional to its
frequency (ν )
It is expressed by the equation, E = hν
Where ‘h’ is known as Planck’s constant and its value is 6.626×10–34 J s.
Photoelectric effect

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 It is the phenomenon of ejection of electrons by certain metals (like
potassium, rubidium, caesium etc.) when light of suitable frequency
incident on them. The electrons ejected are called photoelectrons. This
phenomenon was first observed by H.Hertz. The important characteristics
of photoelectric effect are:
1. 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.
2. The number of electrons ejected is proportional to the intensity or
brightness of light.
3. For each metal, there is a minimum frequency (known as
threshold frequency [ν0]) below which photoelectric effect is not
observed.
4. The kinetic energy of the ejected electrons is directly proportional
to the frequency of the incident light.
Explanation of photoelectric effect
A satisfactory explanation to photoelectric effect was first given by
Albert Einstein using Planck’s Quantum theory. According to him, when a
photon of sufficient energy strikes the metal surface, it transfers its energy
to the electron of the atom of the metal instantaneously and the electron is
ejected without any time lag. A part of the energy is used to eject the
electron from the metal surface (i.e. to overcome the attractive force of the
nucleus [work function, hν0]) and the other part is given to the ejected
electron in the form of kinetic energy. Greater the energy possessed by the
photon, greater will be transfer of energy to the electron and greater the
kinetic energy of the ejected electron.
Since the striking photon has energy equal to hν and the minimum
energy required to eject the electron is hν0 (also called work function, W0)
then the difference in energy (hν – hν0) is transferred as the kinetic energy
of the photoelectron.
Following the law of conservation of energy principle, the kinetic energy
of the ejected electron is given by

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 K.E = hν - hν0
Or, hν = hν0 + ½ mev 2
Where me is the mass of the electron and v is the velocity of the ejected
electron. A more intense beam of light contains larger number of photons,
so the number of electrons ejected is also larger.
Dual Behaviour of Electromagnetic Radiation
Electromagnetic radiations possess both particle and wave nature.
This is known as dual nature of Electromagnetic Radiation.
Atomic spectrum
When a ray of white light is passed through a prism, we get a series
of coloured bands called spectrum. This spectrum is called continuous
spectrum, because here violet merges into blue, blue into green and so on.
Similarly, when electromagnetic radiation interacts with matter,
atoms and molecules may absorb energy and reach to a higher energy
unstable state. To attain stability, they emit radiations in the form of
spectrum. Such a spectrum is called atomic spectrum.
Emission and Absorption Spectra
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”. To produce an emission
spectrum, energy is supplied to a sample by heating it or irradiating it and
the wavelength (or frequency) of the radiation emitted is recorded.
An absorption spectrum is like the photographic negative of an
emission spectrum. Here a continuum of radiation (like white light) is
passed through a sample which absorbs radiation of certain wavelengths.
The missing wavelengths leave dark spaces in the bright continuous
spectrum. The study of emission or absorption spectra is referred to as
spectroscopy.
The emission spectra of atoms in the gas phase do not form a
continuous spectrum. The excited atoms emit light only at specific
wavelengths with dark spaces between them. Such spectra are called line
spectra or atomic spectra.

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 Line emission spectra are very useful in the study of electronic
structure of atoms. 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 finger prints are used to
identify people. So line emission spectra are also called finger print of
atoms.
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. The
hydrogen spectrum consists of several series of lines named after their
discoverers. The first five series of lines are Lyman, Balmer, Paschen,
Brackett and Pfund series. Among these lines, the Balmer series is the
only series that we can be visible (since it lies in the visible region of emr).
Johannes Rydberg proposed an equation for finding the wave
number of the different lines in Hydrogen spectrum.
The expression is:
ῡ = 1/ λ = 109677 (1/n1 2 -1/n2 2 ) cm-1
Where n1 = 1, 2, 3,….. and n2 = n1 + 1, n1 + 2, ……
The different spectral lines, their n1 and n2 values and their spectral region
are:

Series Spectral n1 n2
region
Lyman Ultra violet 1 2,3,4...
Balmer Visible 2 3,4,5..
Paschen Infra red 3 4,5,6..
Brackett Infra red 4 5,6,7..
Pfund Infra red 5 6,7,8..

BOHR’S MODEL FOR HYDROGEN ATOM

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 The general features of the structure of hydrogen atom and its
spectrum was first explained by Niels Bohr. The important postulates of
his theory are:
1. The electron in the hydrogen atom can move around the nucleus
in circular paths of fixed radius and energy. These paths are called
orbits or stationary states or allowed energy states. These energy
levels are numbered as 1,2,3 etc or as K, L, M, N, etc. These
numbers are known as Principal quantum numbers.
2. The energy of an electron in an orbit does not change with time.
However, when an electron absorbs energy, it will move away from
the nucleus (i.e. to a higher energy level) and when it loses energy, it
will move towards the nucleus (i.e. to a lower energy level).
3. The radius of orbits can be given by the equation: rn = a0 n 2 where
a0 = 52.9 pm. Thus the radius of the first stationary state is 52.9 pm
(called the Bohr radius). As n increases, the value of r will increase.
4. The energy of electron in an orbit is given by the expression:
En = -RH (1/n2 ), where n = 1,2,3…… and RH is a constant called
Rydberg constant. Its value is 2.18x10-18 J. The energy of the lowest
state (the ground state) is given by E1 = –2.18×10–18J. As the value
of n increases, the energy of the electron also increases.
5. The frequency of radiation absorbed or emitted when transition
occurs between two stationary states that differ in energy by ΔE, is
given by:
𝛥𝐸 𝐸2 −𝐸1
ν= =
ℎ ℎ

Where E1 and E2 are the energies of lower and higher energy levels
respectively. This expression is commonly known as Bohr’s frequency
rule.
6. The angular momentum of an electron is an integral multiple of
𝑛ℎ
h/2π. i.e. mevr =
2𝜋

Where me is the mass of electron, v is the velocity of electron

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and r is the radius of Bohr orbit. n = 1,2,3......... Thus an electron can move
only in those orbits whose angular momentum is an integral multiple of
h/2π. So only certain fixed orbits are allowed.

Significance of negative energy of electron

When the electron is free from the influence of
nucleus, its energy is taken as zero. In this situation,
the electron is at the orbit with n = ∞. When the
electron is attracted by the nucleus and is present in
orbit n, the energy is emitted and its energy is
lowered. That is the reason for the presence of
negative sign in equation.
Explanation of Line Spectrum of Hydrogen
According to Bohr atom model, radiation is absorbed if the electron
moves from lower energy to higher energy level and radiation is emitted if
the electron moves from higher orbit to lower orbit. The energy gap
between the two orbits is given by equation:

The frequency associated with the absorption and emission of the

photon can be given as

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 In case of absorption spectrum, n2 > n1 and the term in the
bracket is positive and energy is absorbed. On the other hand, in case
of emission spectrum n1 > n2, ΔE is negative and energy is released.
Limitations of Bohr Atom Model: Bohr atom model could explain
the stability and line spectra of hydrogen atom and hydrogen like
ions (e.g. He+ , Li2+, Be3+ etc). But it has the following limitations:
1. It could not explain the fine spectrum of hydrogen atom.
2. It could not explain the spectrum of atoms other than
hydrogen.
3. It was unable to explain the splitting of spectral lines in the
presence of electric field (Stark effect) and in magnetic field
(Zeeman effect).
4. It could not explain the ability of atoms to form molecules
by chemical bonds.
5. It did not consider the wave character of matter and
Heisenberg’s uncertainty principle.
Dual Behaviour of Matter – de Broglie’s equation
de Broglie proposed that like radiation, matter also exhibit dual
behaviour i.e., both particle and wave like properties. This means that
electrons should also have momentum as well as wavelength. He gave the
following relation between wavelength (λ) and momentum (p) of a
material particle.

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 ℎ ℎ
λ= =
𝑚𝑣 𝑝

Where m is the mass of the particle, v is the velocity and p is the

momentum. The above equation is known as de Broglie’s equation.
Just like electromagnetic radiations, an electron beam also undergoes
diffraction. This is an evidence for the wave nature of electrons. An
electron microscope works on the principle of wave nature of electron.
According to de Broglie, every moving object has a wave character.
The wavelengths associated with ordinary objects are so short (because of
their large masses) that their wave properties cannot be detected. The
wavelengths associated with electrons and other subatomic particles (with
very small mass) can be detected experimentally.
Heisenberg’s Uncertainty Principle
Werner Heisenberg proposed the uncertainty principle which is the
consequence of dual behaviour of matter and radiation. It states that “it is
impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of a moving microscopic particle like electron”.
Mathematically, it can be given as in equation:
ℎ
Δx. Δp ≥
4𝜋

ℎ
Or, Δx.mΔv ≥
4𝜋

ℎ
Or, Δx.Δv ≥
4𝜋𝑚

Where Δx is the uncertainty in position and Δp (or, Δv) is the uncertainty

in momentum (or velocity) of the particle.
If the position of the electron is known with high degree of accuracy (Δx is
small), then the velocity of the electron will be uncertain [Δv is large] and
vice versa.

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Significance of Uncertainty Principle
Heisenberg Uncertainty Principle is significant only for motion of
microscopic objects and is not applicable to macroscopic objects.
According to this Principle, we cannot determine the exact position and
momentum of an electron. Thus it rules out the existance of definite paths
or orbits of electrons. We can only say the probability of finding an
electron at a given point.
Reasons for the Failure of the Bohr Model
In Bohr model, electrons are moving in well defined circular orbits
about the nucleus. The wave character of the electron is not considered in
Bohr model. Further, 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 uncertainty principle. Therefore, Bohr model of the
hydrogen atom not only ignores dual behaviour of matter but also
contradicts Heisenberg uncertainty principle.
QUANTUM MECHANICAL MODEL OF ATOM
On the basis of dual nature of matter and the uncertainty principle,
Erwin Schrodinger and Werner Heisenberg proposed a new model of atom
called Quantum mechanics. The fundamental equation of quantum
mechanics was developed by Schrödinger and is known as Schrödinger
equation. It is written as:
Ĥ ψ = Eψ
where Ĥ is a mathematical operator called Hamiltonian operator, E is the
total energy of the system (K.E + P.E) and ψ is called the wave function.
On solving the above equation, we get different values for E and ψ.
When Schrödinger equation is solved for hydrogen atom, the
solution gives the possible energy levels the electron can occupy and the
corresponding wave function (ψ). These quantized energy states and
corresponding wave functions are characterized by a set of three quantum
numbers.
Significance of ψ

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 The wave function (ψ) is a mathematical function and it has no
physical meaning. Wave functions of hydrogen or hydrogen like species
with one electron are called atomic orbitals. All the information about the
electron in an atom is stored in its orbital wave function ψ. It may be
positive or negative.
But ψ2 has some physical significance. It gives the probability of
finding an electron at a point within an atom. So ψ2 is known as
probability density and is always positive. From the value of ψ2 , it is
possible to predict the probability of finding the electron around the
nucleus.
Quantum Numbers
These are certain numbers used to explain the size, shape and
orientation of orbitals. Or, Quantum numbers are the address of an
electron. There are four quantum numbers which describe the electron in
an atom. They are Principal Quantum number (n), Azimuthal Quantum
number (Ɩ), Magnetic Quantum number (m or mƖ) and Spin Quantum
number (s)
1. Principal Quantum Number (n)
The following informations are obtained from n.
1. It gives the size the orbit.
2. It gives the energy of electron in an orbit.
3. It gives the shell in which the electron is found.
4. It also gives the average distance between the electron and the
nucleus. As the value of n increases, the distance between the
electron and the nucleus also increases.
The possible values of n are 1, 2, 3, 4, 5 etc.
If n = 1 the electron is in K shell
n = 2 the electron is in L shell
n = 3 the electron is in M shell and so on.
2. Azimuthal Quantum Number [Subsidiary or orbital angular
momentum Quantum number] (Ɩ)

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 The following informations are obtained from Ɩ.
1. It gives the shape of the orbital.
2. It gives the sub shell or sub level in which the electron is located.
3. It also gives the orbital angular momentum of the electron.
For a given value of n, Ɩ can have n values ranging from 0 to n – 1. That is,
for a given value of n, the possible value of Ɩ are : Ɩ = 0, 1, 2, .......... (n-1).
For example, when n = 1, value of Ɩ is only 0. For n = 2, the possible
value of Ɩ can be 0 and 1. For n = 3, the possible Ɩ values are 0,1 and 2.
Ɩ= 0 represents s orbital, Ɩ = 1 represents p orbital, Ɩ = 2 represents d
orbital and Ɩ = 3 represents f orbital
The number of sub shells in a principal shell is equal to the value of n. For
example,
When n = 1, Ɩ= 0. i.e. K shell contains only one sub shell - s sub shell
when n = 2, Ɩ = 0 and1. i.e. L shell contains two sub shells - s and p
sub shells
when n = 3, Ɩ = 0, 1 and 2. i.e. M shell contains three sub shells – s, p
and d sub shells
when n = 4, Ɩ = 0, 1, 2 and 3. i.e. N shell contains four sub shells – s,
p,d and f sub shells
3. Magnetic Quantum Number (m or mƖ)
It gives information about the orientation of orbitals in space. For a
given ‘Ɩ’ value, there are 2Ɩ+1 possible values for m and these values are
given by :
m = – Ɩ to 0 to + Ɩ
Thus for Ɩ = 0, mƖ = 0 [2(0)+1 = 1].. i.e. s sub shell contains only one
orbital called s orbital.
For Ɩ = 1, mƖ = –1, 0 and +1 [2(1)+1 = 3]. i.e. p subshell contains three
orbitals called p orbitals (px, py and pz).
For Ɩ = 2, mƖ = –2, –1, 0, +1 and +2, [2(2)+1 = 5]. i.e. d subshell contains
five orbitals called d orbitals (dxy, dxz, dyz, dx 2 - y 2 and dz 2 )

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4. Spin Quantum Number (s or ms)
It is the only experimental Quantum number and it gives the spin
orientation of electrons. This spin may be either clockwise or
anticlockwise. So the values for s may be +½ or -½. +½ represents clock-
wise spin and-½ represents anticlock -wise spin.
Shapes of orbitals
1. s-orbitals
For s-orbitals, Ɩ = 0 and hence mƖ = 0. So there is only one
possible orientation for s orbitals. They are spherically symmetrical.
The plots of probability density (ψ2 ) against distance from the
nucleus (r) for 1s and 2s atomic orbitals are as follows:

For 1s orbital the probability density is maximum at the nucleus and

it decreases with increase in r. But for 2s orbital the probability density
first decreases sharply to zero and again starts increasing. After reaching a
small maximum it decreases again and approaches zero as the value of r
increases. The region where the probability density (ψ2 ) reduces to zero is
called nodal surface or node.
For 1s orbital, there is no node, for 2s orbital there is only one node,
for 3s orbital there are 2 nodes and so on. In general, for an ns-orbital there
are (n – 1) nodes.
All the s-orbitals are spherically symmetrical and their size increases
with increase in n. The boundary surface diagrams for 1s, 2sand 3s orbitals
are as follows:

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 2. p-orbitals
For p-orbitals, Ɩ = 1 and mƖ = -1, 0, +1. i.e., there are three possible
orientations for p orbitals. So there are 3 types of p-orbitals – px, py and pz.
Each p orbital consists of two lobes. The probability density function is
zero on the plane where the two lobes touch each other.

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Rules for Filling of electrons in various orbitals
The filling of electrons into the orbitals of different atoms takes
place according to the 3 rules - aufbau principle, Pauli’s exclusion
principle and the Hund’s rule of maximum multiplicity.
1. Aufbau principle:
The German word aufbau means ‘build up’. The building up of
orbitals means the filling up of orbitals with electrons. It states that the
orbitals are filled in order of their increasing energies. In other words,
electrons first occupy the lowest energy orbital and then to higher energy
orbitals.
This rule has two sub rules:
a) The various orbitals are filled in the increasing order of their (n+Ɩ)
value.

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 b) If two orbitals have the same (n+Ɩ) values, the orbital with the
lower n value is filled first.
The increasing order of orbitals is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s...

2. Pauli’s Exclusion Principle

It states that no two electrons in an atom can have the same set of
four quantum numbers. i.e. an orbital can accommodate a maximum of
only 2 electrons with opposite spin.
If 2 electrons have same values for n, Ɩ and m, they should have
different values for s. i.e. if s = +½ for the first electron, it should be -½ for
the second electron.
3. Hund’s rule of maximum multiplicity
It states that electron pairing takes place only after partially filling all
the degenerate orbitals. Orbitals having same energies are called
degenerate orbitals. For example the electronic configuration of N is
1s2 2s2 2px1 py1 pz1 and not 1s2 2s2 2px2 py1 .
Electronic Configuration of Atoms
The distribution of electrons into various orbitals of an atom is
called its electronic configuration. The electronic configuration of different
atoms can be represented in two ways.
(i) sa p b d c ...... notation
(ii) Orbital diagram
The electrons in the completely filled shells are known as core
electrons and the electrons in the outer most shell are called valence
electrons.
Stability of Completely Filled and Half Filled Subshells
For atoms having half filled or completely filled electronic
configurations have extra stability compared to other atoms. This is due to

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their symmetrical distribution of electrons and greater exchange energy.
For example, the electronic configuration of Cr is [Ar] 3d5 4s1 and not 3d4
4s2 . This is because d5 represents a half filled configuration and has extra
stability. Similarly for Cu the electronic configuration is [Ar] 3d104s1 and
not 3d9 4s2 .

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