Chapter-2

Structure of Atom
Introduction

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

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

Atomic Structure

Atom is made up of smaller units like proton, neutron and electron. Some other particles like
positron, neutrino, antineutrino, π-meson, μ-meson, k meson etc are also present which are very
short lived.
Discovery of Electron

In 1879, William Crooks studied the conduction of electricity through gases at low pressure.
He performed the experiment in a discharge tube which is a cylindrical hard glass tube about
60 cm in length. It is sealed at both the ends and fitted with two metal electrodes. The electrical
discharge through the gases could be observed only at very low pressures and at very high
voltages.

J.J. Thomson took a discharge tube and applied a voltage of a 10000 Volt potential difference
across it at a pressure of 10–2 mm of Hg. He found some glowing behind anode. It means some
invisible rays produced at cathode strike behind anode and produce fluorescence. He named
them cathode rays.

Properties of Cathode Rays

1) These rays have mechanical energy and travel in straight line.
2) These rays are deflected towards positive plate of electric field. It means these are
made up of negatively charged particle called electron.
3) Colour observed is independent from nature of gas.
4) Mullikan determined the charge on electron which is 1.602 × 10–19 C.
5) Specific charge on electron is calculated by J.J. Thomson.

Charge to mass ratio

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

According to Thomson, the amount of deviation of the particles from their path in presence of
electrical and magnetic field depends on

1. Magnitude of the negative charge on particle

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

By carrying out accurate measurements on the number of deflections observed by the electrons
on the electric field strength or magnetic field strength, Thomson was able to determine the
value of

𝒆
= 1.758820 x 1011 C kg-1
𝒎𝒆

Where, me = Mass of the electron in kg, e = magnitude of charge on the electron in coulomb (C).

Discovery of Proton

In 1886, Goldstein modified the discharge tube by using a perforated cathode. On reducing the
pressure, he observed a new type of luminous rays passing through the holes or perforations of
the cathode and moving in a direction opposite to the cathode rays. These rays were named as
positive rays or anode rays or as canal rays. Anode rays are not emitted from the anode but
from a space between anode and cathode.

Properties of anode rays

1. These rays deflect towards negative plate of applied electric field. It means these are
made up of positively charged particle.
2. Property of anode rays depends on nature of gas.
3. These rays travel in straight line and have mechanical energy.
Discovery of Neutron

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

9 + 2He4 ⟶ 6C12 + 0n1

4Be

Neutron is chargeless particle and have mass equal to proton.

Some Uncommon Subatomic Particles

1. Positron Positive electron (0+1e), discovered by Dirac (1930) and Anderson (1932).
2. Neutrino and antineutrino Particles of small mass and no charge as stated by Fermi
(1934).
3. Meson Discovered by Yukawa (1935) and Kemmer. They are unstable particles and
include pi ions [pi;+, pi;– or pi;0].
4. Anti-proton It is negative proton produced by Segre and Weigand (1955).

Millikan’s Oil Drop Experiment

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

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

J.J. Thomson in 1898, proposed a model of atom which looked more or less like plum pudding
or raisin pudding. He assumed atom to be a spherical body in which electrons are unevenly
distributed in a sphere having positive charge which balance the electron’s charge. It is called
Plum pudding model.

Important Feature of This Model: The mass of the atom is assumed to be uniformly
distributed over whole atom.

Drawbacks:

This model was able to explain the overall neutrality of the atom, it could not satisfactorily,
explain the results of scattering experiments carried out by Rutherford in 1911.

Rutherford's Model

Rutherford in 1911, performed some scattering experiments in which he bombarded thin foils
of metals like gold, silver, platinum or copper with a beam of fast moving a-particles. The thin
gold foil had a circular fluorescent zinc sulphide screen around it. Whenever a-particles struck
the screen, a tiny flash of light was produced at that point.

From these experiments, he made the following observations:

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

2. Few particles deviate with small angle.
3. Rare particles retrace its path or show deflection greater than 90°.
On the basis of these observation, he proposed a model:

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

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

Drawback:

This model could not explain stability of atom. According to Maxwell's classic theory, an
accelerated charged particle liberates energy. So, during revolution, it must radiate energy and
by following the spiral path it should comes on nucleus.

Atomic number

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

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

Mass number

It is equal to the sum of the positively charged protons (p) and electrically neutral neutrons (n).
Mass number of an atom is designated by the letter ‘A’.

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

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

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

Characteristics of Isotope

a) Since, the isotopes differ in their atomic masses, all the properties of the isotopes
depending upon the mass are different.
b) Since, the chemical properties are mainly determined by the number of protons in the
nucleus, and the number of electrons in the atom, the different isotopes of an element
exhibit similar chemical properties. For example, all the isotopes of carbon on burning
give carbon dioxide.

Isobars

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

Electromagnetic Waves Theory

This theory was put forward by James Clark Maxwell in 1864. Electromagnetic Waves are the
waves which are produced by varying electric field and magnetic field which are perpendicular
to each other in the direction perpendicular to both of them.
The main points of this theory are as follows:

1. The energy is emitted from any source continuously in the form of radiations and is
called the radiant energy.

2. The radiations consist of electric and magnetic fields oscillating perpendicular to each
other and both perpendicular to the direction of propagation of the radiation.

3. The radiations possess wave character and travel with the velocity of light 3 x
108 m/sec.

4. These waves do not require any material medium for propagation. For example, rays
from the sun reach us through space which is a non-material medium.
Characteristics of a Wave:

 Wavelength (λ): It is the distance between two consecutive crests or troughs and is
denoted by λ.
 Frequency (v): It is the number of waves passing through a given point in one
second. The unit frequency is hertz or cycle per second.
 Wave number: It is the number of waves in a unit cycle. wave number =1λ=1λ
 Velocity: Velocity of a wave is defined as the linear distance travelled by the wave in
one second. It is represented by c and is expressed in m/sec.
 Amplitude: Amplitude of a wave is the height of the crest or the depth of the through.
It is represented by V and is expressed in the units of length.
 Speed of light (c): Wavelength (λ), frequency(v) and speed of light(c) of any
electromagnetic radiations are related to each other as

𝑪 = 𝝀 .𝝂 𝐂 = 𝟑 × 𝟏𝟎𝟖 𝒎/𝒔

Black Body Radiations

Black-body is an ideal body which emits and absorbs radiations of all frequencies. The
radiation emitted by these bodies is called black-body radiation.

At a given temperature, the intensity and frequency of the emitted radiation depends is
temperature. At a given temperature, the intensity of radiation emitted increases with decrease
of wavelength.
Planck's Theory

According to this theory, energy cannot be absorbed or released continuously but it is emitted
or released in the form of small packets called quanta. In case of light this quanta is known
as photon. This photon travels with speed of light. Energy of the photon is directly proportional
to frequency.

𝑬∝𝒗
For 1 photon,
𝒉𝒄
𝑬 = 𝒉𝒗 =
𝝀

For n photons,

𝒉𝒄
𝑬 = 𝒏𝒉𝒗 = 𝒏
𝝀

Where, h is Planck's constant, h = 6.62 × 10–34 J-s

Photoelectric Effect

When light of a suitable frequency is allowed to incident on a metal, ejection of electrons take
place. This phenomenon is known as photo electric effect.

Observations in Photoelectric Effect

1) The minimum energy required to remove the electron from the surface of metal is
known as work function (Φ)
2) Only photons of light of certain minimum frequency called threshold frequency (v0)
can cause the photoelectric effect. The value of v0 is different for different metals.
3) The kinetic energy of the electrons which are emitted is directly proportional to the
frequency of the striking photons and is quite independent of their intensity.
4) The number of electrons that are ejected per second from the metal surface depends
upon the intensity of the striking photons or radiations and not upon their frequency.
Explanation of Photoelectric Effect
a) Einstein in (1905) was able to give an explanation of the different points of the
photoelectric effect using Planck’s quantum theory as under:
b) Photoelectrons are ejected only when the incident light has a certain minimum
frequency (threshold frequency (vo)).
c) If the frequency of the incident light (v) is more than the threshold frequency (v0), the
excess energy (hv – hv0) is imparted to the electron as kinetic energy.
d) On increasing the intensity of light, more electrons are ejected but the energies of the
electrons are not altered.

𝟏
K.E. of the ejected electron. 𝑲𝑬 = 𝒎𝒗𝟐
𝟐

𝑲𝑬 = 𝑬𝒑 − 𝝓
𝑲𝑬 = 𝒉𝝂 − 𝒉𝝂𝒐

𝒉𝒄 𝒉𝒄
𝑲𝑬 = −
𝝀 𝝀𝒐

Bohr’s Model
Niels Bohr in 1913, proposed a new model of atom on the basis of Planck’s Quantum
Theory. The main points of this model are as follows:
1) Atom is of spherical shape having size (of order 10–10 metre).
2) Whole mass is concentrated in centre called nucleus (having order of size 10–
15
metre).
3) Electron revolves around nucleus only in limited circular path and he assumed that
electron does not radiate energy during its revolution in permitted paths.
4) Only those orbits are allowed whose orbit angular momentum is integral multiple
of .

𝒉
𝒎𝒗𝒓 = n where n = 1, 2, 3, 4...
𝟐𝝅

5) When electron absorbs energy, it jumps to higher orbit and when it comes back, it
radiates or emits energy. This postulate explains spectra.
Calculation of Energy, radius and Velocity of electron in Bohr’s Orbit: -
𝒉
𝒎𝒗𝒓 = n
𝟐𝝅

𝒁𝒆𝟐 𝒎𝒗𝟐
𝒌 𝟐 =
𝒓 𝒓

Radius of Bohr’s orbit:

𝒏𝟐 𝒉𝟐
𝒓𝒏 =
𝟒𝝅𝟐 𝒎𝒆𝟐 𝒌𝒁

Where n = Orbit number, m = mass of electron, e = charge on the electron, Z = Atomic

number of element, h= Plank’s constant, K = Coulombic constant. After putting values of h,
m, e, k we get

𝒏𝟐
𝒓𝒏 = 𝟎. 𝟓𝟐𝟗 Å
𝒁

Velocity of electron in Bohr’s orbit:

𝟐𝝅𝒆𝟐 𝒁𝑲
𝐯𝒏 =
𝒏𝒉

Where n = Orbit number, e = charge on the electron, Z = Atomic number of element, h=

Plank’s constant, K = Coulombic constant. After putting values of h, e, k we get

𝒁
𝐯𝒏 = 𝟐. 𝟏𝟖 × 𝟏𝟎𝟔 𝐦/𝐬
𝒏

Energy of electron in Bohr’s orbit:

Total energy of electron = K.E. + P.E. of electron

𝑲𝒁𝒆𝟐 𝑲𝒁𝒆𝟐 𝑲𝒁𝒆𝟐

= + − 𝟐𝒓 = − 𝟐𝒓
𝟐𝒓

Substituting value of r, we get: -

𝟐𝝅𝟐 𝒎𝒆𝟒 𝒁𝟐 𝑲𝟐
𝑬=−
𝒏𝟐 𝒉𝟐

Where n = Orbit number, e = charge on the electron, Z = Atomic number of element, h= Plank’s
constant, K = Coulombic constant. After putting values of h, e, k we get
 𝟏𝟖
𝒁𝟐
𝐄𝒏 = −𝟐. 𝟏𝟖 × 𝟏𝟎 𝐉/𝐚𝐭𝐨𝐦
𝒏𝟐

𝒁𝟐
𝐄𝒏 = −𝟏𝟑. 𝟔 𝟐 𝐞𝐕/ 𝐚𝐭𝐨𝐦
𝒏

𝒁𝟐 𝟏
𝐄𝒏 = −𝟏𝟑𝟏𝟐 𝟐 𝑲𝐉 𝐦𝐨𝐥
𝒏

𝟏𝟗
1eV = 1.6× 𝟏𝟎 J
1Cal = 4.18 J
1J = 107 erg

When an electron jumps from an excited state (higher orbit) n2 to an inner orbit n1 then the
energy emitted in the form of radiation is given by

∆𝑬 = 𝑬𝟐 − 𝑬𝟏

𝟏 𝟏
∆𝑬 = 𝟏𝟑. 𝟔 𝒁𝟐 − 𝒆𝑽/𝐚𝐭𝐨𝐦
𝒏𝟐𝟏 𝒏𝟐𝟐

Achievements of Bohr’s Theory

1) Bohr’s theory has explained the stability of an atom.
2) Bohr’s theory has helped in calculating the energy of electron in hydrogen atom and
one electron species.
3) Bohr’s theory has explained the atomic spectrum of hydrogen atom.

Limitations of Bohr’s Model

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

Sommerfeld Extension to Bohr’s Model

According to this theory. the angular momentum of revolving electron in all elliptical orbit is
𝒉
an integral multiple of h / 2π, i.e., 𝒎𝒗𝒓 = n 𝟐𝝅
𝒉
From Bohr model, 𝒎𝒗𝒓 = n 𝟐𝝅
For, K shell. n = 1, Circular shape L shell. n = 1,2, Circular
M shell, n = 1.2.3 Elliptical N shell. n = 1,2,3,4 Elliptical
Spectrum
1. The most compelling evidence for the quantization of energy comes from
spectroscopy. Spectrum word is taken from Latin word which means appearance. The
record of the intensity transmitted or scattered by a molecule as a function of
frequency or wavelength is called its spectrum. OR
2. When a ray of white light is passed through a prism the wave with shorter
wavelength bends more than the one with a longer wavelength. Since ordinary
white light consists of waves with all the wavelengths in the visible range, array of
white light is spread out into a series of colours called spectrum.
3. The light of red colour which has longest wavelength is deviated the least while the
violet light, which has shortest wavelength is deviated the most.

4. Continuous Spectrum
When a ray of white light is analysed by passing through a prism it is observed that it
splits up into seven different wide bands of colours from violet to red (like rainbow).
These colours are so continuous that each of them merges into the next. Hence, the
spectrum is called continuous spectrum.

5. Emission Spectrum
Emission Spectra is noticed when the radiations emitted from a source are passed
through a prism and then received on the photographic plate. Radiations can be
emitted in a number of ways such as:
(i) from sun or glowing electric bulb.
(ii) by passing electric discharge through a gas at low pressure.
(iii) by heating a substance to high temperature.

6. Line Spectrum
When the vapours of some volatile substance are allowed to fall on the flame of a
Bunsen burner and then analysed with the help of a spectroscope. Some specific
coloured lines appear on the photographic plate which are different for different
substances. For example, sodium or its salts emit yellow light while potassium or its
salts give out violet light.

7. Absorption Spectrum
When white light is passed through the vapours of a substance and the transmitted
light is then allowed to strike a prism, dark lines appear in the otherwise continuous
spectrum. The dark lines indicate that the radiations corresponding to them were
absorbed by the substance from the white light. This spectrum is called absorption
spectrum.

8. Dark lines appear exactly at the same positions where the lines in the emission spectra
appear.
Cosmic rays < gamma rays < x rays < ultraviolet rays < visible rays < infrared
< micro waves < radio waves

Line Spectrum of Hydrogen Atom or (Emission spectrum of Hydrogen)

When electric discharge is passed through hydrogen gas enclosed in discharge tube under low
pressure and the emitted light is analysed by a spectroscope, the spectrum consists of a large
number of lines which are grouped into different series. The complete spectrum is known as
hydrogen spectrum.
On the basis of experimental observations, Johannes Rydberg noted that all series of lines in
the hydrogen spectrum could be described by the following expression:

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

where Z is the atomic number of the species.

Here R = constant, called Rydberg constant (1.1×107 m),

RH = constant, called Rydberg constant for hydrogen and n1, n2 are integers (n2 > n1)
Thus, by substituting the values of n1 and n2 in the above equation, wavelengths and wave
number of different spectral lines can be calculated.
Zeeman Effect
When spectral line (source) is placed in magnetic field, spectral lines split up into sublines.
This is known as zeeman effect.

Stark Effect
If splitting of spectral lines take place in electric field, then it is known as stark effect.

Dual Behaviour of Matter (de Broglie Equation)

De Broglie in 1924, proposed that matter, like radiation, should also exhibit dual behaviour i.e., both
particle like and wave like properties. This means that like photons, electrons also have momentum as
well as wavelength.
Assume light have wave nature, then its energy should be given by Planck's theory
𝒉𝒄
𝑬 = 𝒉𝒗 = 𝝀
…(i)

If it has particle nature, then its energy should be given by Einstein relation
E = mc2 …(ii)

𝒉𝒄
On comparing equation (i) and (ii), 𝑬 = 𝒎𝒄𝟐 =
𝝀

𝒉
𝝀 = 𝒎𝒄 (for light)

𝒉 where, m = mass of particle

For other matter, 𝝀= v = velocity of particle
𝒎𝐯
𝒉
𝝀= where p = momentum
𝒑
 𝒉
Also, 𝝀= where KE = Kinetic energy
𝟐𝒎𝑲𝑬

Heisenberg’s Uncertainty Principle

It states that, "It is impossible to measure simultaneously the exact position and exact
momentum of a microscopic particle".
If uncertainty in position = Δx and uncertainty in momentum = Δp .
When both are measured simultaneously, According to this principle,

𝒉
Δ𝒙 . Δ𝒑 ≥
𝟒𝝅
𝒉
Δ𝒙 . Δ(𝒎𝐯) ≥
𝟒𝝅
𝒉
Δ𝒙 . 𝒎Δ𝐯 ≥
𝟒𝝅

Significance of Uncertainty Principle

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

Reasons for the Failure of Bohr Model

i. The wave character of the electron is not considered in Bohr Model.

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

Quantum Mechanical Model of Atom

1. Quantum mechanics: Quantum mechanics is a theoretical science that deals with the
study of the motions of the microscopic objects that have both observable wave and
particle like properties. This model deals with dual behaviour of matter. It is given by
Werner Heisenberg and Erwin Schrodinger
2. Schrodinger wave equation is

𝝏𝟐 𝜳 𝝏𝟐 𝜳 𝝏𝟐 𝜳
+ + (𝑬 − 𝑼)𝜳 = 𝟎
𝝏𝒙𝟐 𝝏𝒚𝟐 𝝏𝒛𝟐

where, x, y, z = cartesian coordinates, m = mass of electron, E = total energy of electron,

U = potential energy of electron, h =Planck’s constant, Ψ (Psi) = wave function which gives
the amplitude of wave, Ψ2 = probability function
For H-atom. the equation is solved as HΨ = EΨ

where, H is the total energy operator, called Hamiltonian. If the sum of kinetic energy
operator (T) and potential energy operator (U) is the total energy E of the system,

H=T+U (T + U) Ψ = EΨ

The atomic orbitals can be represented by the product of two wave functions
(i) radial wave function
(ii) angular wave function.
The orbital wave function, Ψ has no significance, but Ψ2 has significance, it measures the
electron probability density at a point in an atom. Ψ can he positive or negative but ‘I’ is
always positive.

Important Features of Quantum Mechanical Model of Atom

a) The energy of electrons in atom is quantized i.e., can only have certain values.
b) The existence of quantized electronic energy level is a direct result of the wave like
properties of electrons.
c) Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously.
d) An atomic orbital has wave function φ. There are many orbitals in an atom. Electron
occupy an atomic orbital which has definite energy. An orbital cannot have more than
two electrons. The orbitals are filled in increasing order of energy. All the information
about the electron in an atom is stored in orbital wave function φ.
e) The probability of finding electron at a point within an atom is proportional to square
of orbital wave function i.e., |φ2|at that point. It is known as probability density and is
always positive.
f) From the value of φ2 at different points within atom, it is possible to predict the region
around the nucleus where electron most probably will be found.

Probability Diagrams
The graph plotted between Ψ2 and distance from nucleus is called probability diagrams.

A region or space, where probability of finding an electron is maximum is called a

peak, while the probability of finding electron is zero is called node.
 Nodes are of two types:
(a) Radial nodes - The spherical surfaces around the nucleus where the probability of
finding an electron is zero are called radial nodes. Radial node = (n – l - 1)

(b) Angular nodes - The planes or planar areas around the nucleus where the probability
of finding an electron is zero are called angular nodes. Angular node = ( l )

Total node = Radial node + Angular node

= (n - l - 1) + (l)

= (n - 1)

Number of Peaks and Nodes for Various Orbitals

S. No. Type of orbital Number of peaks

1 s n n–1

2 p n–1 n–2

3 d n–2 n–3

4 f n–3 n–4

Quantum Numbers

There are a set of four quantum numbers which specify the energy, size, shape and orientation
of an orbital. To specify an orbital only three quantum numbers are required while to specify
an electron all four quantum numbers are required.

(i) Principal quantum number (n)

It is denoted by n. It tells us about the main shell in which electron resides. It also gives an
idea about the energy of shell and average distance of the electron from the nucleus.
Value of n = any integer. (n = 1,2,3………..).

(ii) Azimuthal quantum number (l)

It is denoted by l. It tells about the number of subshells (s, p, d, f) in any main shell. It also
represent the angular momentum of an electron and shapes of subshells.
𝒉
The orbital angular momentum of an electron = √𝒍(𝒍 + 𝟏) 𝟐𝝅
Value of l = 0 to n – 1.

For, l = 0 (s) for, l =1 (p) for, l =2 (d) for, l =3 (f) and so on

Number of subshells in main energy level = n.
(iii) Magnetic quantum number (m)
It is denoted by m. It tells about the number of orbitals and orientation of each subshell.
Value of m = – l to + 1 including zero.
Number of orbitals in each subshell = (2l + 1)
Ex: - n = 2, l = 1, m = -1,0,1

S. No. Sub-shell (l) Orbital (m)

1. s 1 (0)
2. p 3 (-1,0,1)
3. d 5(-2, -1, 0, 1, 2)
4. f 7(-3, -2, -1, 0, 1, 2, 3)

Number of orbitals in main energy level = n2

(iv) Spin quantum number (ms or S)

𝟏 𝟏
It refers to orientation of the spin of the electron. It can have two values + 𝟐 and − 𝟐 .
𝟏 𝟏
+ 𝟐 identifies the clockwise spin and − 𝟐 identifies the anti-clockwise spin.

𝟏
Example – n =3, l = 2, m = -1, S = − 𝟐
Maximum number of electrons in main energy level = 2n2

Difference between Orbit and Orbital

Shape of Atomic Orbitals

(i) Shapes of s-orbitals

s-orbital is present in the s-subshell. For this subshell, l = 0 and ml = 0. Thus, s-orbital with
only one orientation has a spherical shape with uniform electron density along all the three
axes. The probability of finding electron is found to be maximum near the nucleus and
decreases with the increase in the distance from the nucleus.
(ii) Shapes of p-orbitals

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

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

(iii). Shapes of d-orbitals

d-orbitals are present in d-subshell for which l = 2 and ml = -2, -1, 0, +1, +2. This means that
there are five orientations leading to five different orbitals.
Electronic Configuration
Arrangement of electrons in the space around nucleus in an atom known as electronic
configuration or Distribution of electron in various orbitals is known as electronic
configuration.
The electrons filled in orbitals must obey the following rules -

1. Aufbau’s principle
2. Pauli’s exclusion principle
3. Hund’s rule of maximum multiplicity

1. Aufbau’s principle
According to this principle, in the ground state of an atom, the electrons occupy the lowest
energy orbitals available to them, i.e.,
a) the orbitals are filled in order of increasing value of n + l.
b) For the orbitals having the same value of n + 1, the orbital having lower value of n is
filled up first.

The general order of increasing energies of the orbital is

The energy of atomic orbitals for H-atom varies as

1s < 2s = 2p < 3s 3p = 3d < 4s = 4p = 4d = 4f
Half-filled and completely filled electronic configurations are more stable Hence. outer
configuration of Cr is 3d5 4s1 and Cu is 3d10 4s1.

(ii) Pauli’s exclusion principle

It states, no two electrons in an atom can have identical set of four quantum numbers.
The maximum number of electrons in s subshell is 2, p subshell is 6 d subshell is 10 and f
subshell is 14.
In the same orbital, electron always accommodate in opposite spins. An orbital can have a
maximum of two electrons, with opposite spin.

(iii) Hund’s rule of maximum multiplicity

It states that: Pairing of electrons in the orbitals belonging to the same subshell (p, d or f)
does not take place until each orbital belonging to that subshell has got one electron each i.e.,
it is singly occupied.
The unpaired electrons present in the various orbitals of the same subshell should have
parallel spins.
Methods of Writing Electronic Configuration
(i) Orbital method- In this, the electrons present in respective orbitals are denoted.
e.g. Cl (17) = 1s2, 2s2, 2p6, 32, 3p5.

(ii) Shell method- In this, the number of electrons in each shell is continuously written. e.g.,
Cl (17) =

(iii) Box method- In this method, each orbital is denoted by a box and electrons are
represented by half-headed (↑) or full-headed (↑) arrows. An orbital can occupy a maximum
of two electrons.
e.g.,

Electronic Configuration of Ions

To write the electronic configuration of ions. first write the electronic configuration of neutral
atom and then add (for negative charge) or remove (for positive charge) electrons in outer
shell according to the nature and magnitude of charge present on the ion. e.g:
O (8) = 1s2,2s2 2p4
O2- (10) = 1s2,2s2, 2p6

Causes of Stability of Completely Filled and Half Filled Subshells

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

1. Symmetrical distribution of electrons: The completely filled or half-filled subshells have

symmetrical distribution of electrons in them and are therefore more stable.
2. The stabilizing effect arises whenever two or more electrons with same spin are present
in the degenrate orbitals of a subshell. These electrons tend to exchange their positions
and the energy released due to their exchange is called exchange energy. The number of
exchanges that can takes place is maximum when the subshell is either half filled or
completely filled.
-As a result the exchange energy is maximum and so is the stability.
Summary
1) Atomic number: It is equal to the number of protons in the nucleus of an atom.
2) Mass number: It is equal to the sum of the positively charged protons (p) and electrically
neutral neutrons (n).
3) Isotopes: Isotopes are the atoms of the same element which have the same atomic number
but different mass numbers.
4) Isobars: are the atoms of different elements having the same mass number but different
atomic numbers.
5) Isoelectronic species: These are those species which have same number of electrons.
6) Radiations: These are defined as the emission or transmission of energy through space in
the form of waves.
7) Electromagnetic waves: The waves which consist of oscillating electric and magnetic
fields are called electromagnetic waves.
8) Electromagnetic radiations: Those radiations which are associated with electric and
magnetic field are called electromagnetic radiations.
9) Electromagnetic spectrum: The arrangement of the various types of electromagnetic
radiations in the order of increasing or decreasing wavelengths or frequencies is known as
electromagnetic spectrum.
10) Wavelength (λ): It is the distance between successive points of equal phase of a wave.
11) Frequency (𝒗): The number of waves that pass a given point in one second is known as
the frequency.
12) Time period (T): Time taken by the wave for one complete cycle or vibration is called
time period.
13) Velocity (v): It is the distance travelled by a wave in one second.
14) Wave number: It is defined as the number of wavelengths per unit length.
15) Threshold frequency: It is the minimum frequency of light needed to cause the
photoelectric effect.
16) Continuous spectrum: The combination of light of different frequencies in continuous
manner is called continuous spectrum.
17) Line spectrum: The spectrum of atoms consist of sharp well-defined lines corresponding
to definite frequencies is called line spectrum.
18) Spectroscopy: The study of emission or absorption spectra is called spectroscopy.
19) Quantization: The restriction of a property to discrete values and not continuous values is
called quantization.
20) Quantum mechanics: The branch of science that takes into account the dual behaviour of
matter is called quantum mechanics.
21) Atomic orbital: It is the region of space where the probability of finding the electron is
maximum.
22) Quantum numbers: may be defined as a set of four numbers with the help of which we
can get complete information about electron in an atom.
23) Isotones: Species having same number of neutrons are called isotopes,
e.g., 1H3 and 2He4 are isotones.
24) Isodiaphers: Species with same isotopic number are called Isodiaphers, e.g., 19K39, 9F19
25) Isostere: Species having same number of atoms and same number of electrons, are called
isostere, e.g., N2 and CO.