Chapter – 2 rbdr ATOMIC STRUCTURE

FUNDAMENTAL PARTICLES OF ATOM:

Particle Symbol Relative charge Actual charge (coulomb) Mass (kg)

Electro -1 e 0 -1 -1.602 x 10-19 9.1091 x 10-31
n 1H
1 +1 +1.602 x 10-19 1.6725 x 10-27
Proton 0n1 0 0 1.6748 x 10-27
Neutron

ATOMIC NUMBER: The number of protons present in the nucleus of an atom of a particular element is known as
atomic number (Z).

MASS NUMBER: The sum of the number of protons and neutrons in the nucleus of an atom is called as the mass
number (A).

CALCULATION OF NUMBER OF NEUTRONS IN AN ATOM:

Number of neutrons = Mass number – Atomic number = A - Z

e.g. : The number of neutrons in 6C14

Number of neutrons = Mass number – Atomic number = A - Z = 14 – 6 = 8

ISOTOPES: Atoms of an element with same number of protons but different number of neutrons are called
isotopes.
e.g. : 1H1 (Protium), 1H2 (Deuterium) and 1H3 (Tritium) are the isotopes of Hydrogen.

WAVE NATURE OF LIGHT: Huygen proposed the wave nature of light to explain the properties of interference and
diffraction. Later in 1856, Maxwell proposed that light and other forms of radiant energy like  rays, X-rays, U.V.
rays, visible rays I.R. rays travel as waves through space. They are called electro-magnetic radiation or waves,
because they have both electric and magnetic fields associated with it.
A wave is a periodic disturbance in space and a wave motion represents the propagation of this
disturbance, which carries energy.

Crest λ Crest

Amplitude

Direction of propagation
Point of disturbance

Trough Trough

A wave is characterised by the following parameters.

(i) Wave length (λ): It is the distance between two consecutive crests or two consecutive troughs in a wave.
It is generally measured in Angstrom (A0) or nanometers (nm).
Atomic Structure rbdr 9
0 -10 -9
1A = 10 m. 1 nm = 10 m.

(ii) Frequency (υ): It is the number of waves passing through a given point in one second. It is expressed in
cycles per second (cps), sec-1 or Hertz (Hz).
1 Hertz = 1 cycle per second = sec-1

(iii) Velocity (c): It is the distance traveled by a wave in one second.

The velocity of all electro magnetic radiation is equal to the velocity of light i.e., 3 x 108 m sec-1.
The velocity ‘c’ of a wave is related to its frequency ‘υ’ by the following relation:

c=υλ

(iv) Amplitude (a): It is the height of the crest or the depth of the trough of a wave. The intensity or
brightness of radiation is determined by amplitude.

(v) Wave number ( υ ): It is the number of wave lengths in a unit length. It is expressed in cm-1 or m-1.
Wavelength of a wave is the reciprocal of its wavelength.

υ=1 Since λ =c Therefore, υ = υ

λ υ c

ELECTROMAGNETIC SPECTRUM: It is the arrangement of different types of electro magnetic radiations in the
order of increasing frequency or decreasing wavelength.

Frequency (energy) increases →

5 8
Frequency (Hz) → 10 10 1011 1014 1017 1020 1023 1026
V
Radio Micro Infra red I Ultra violet X-rays γ-rays Cosmic rays
Waves Waves S
I
B
L
Wave length (m) → 103 100 10-3 10-6 E 10-9 10-12 10-15 10-18

Wavelength decreases →

PLANCK’S QUANTUM THEORY: Max Planck proposed the quantum theory of radiation. The important postulates
are:
1. Electro magnetic radiations are emitted propagated or absorbed discontinuously in the form small packets
of energy known as ‘quanta’ or ‘photons’.

2. Each quantum of radiation is associated with a definite amount of energy depending upon the frequency of
radiation. The energy ‘E’ of a quantum is given by,
E=hυ
where ‘υ’ is the frequency of the emitted radiation and ‘h’ is Planck’s constant of
-34
numerical value 6.626 x 10 J s.

3. A body can emit or absorb energy only in integral multiples of quantum. Thus radiant energy can only be
Atomic Structure 10
emitted as hυ, 2hυ and so on.
SPECTRUM: A spectrum is an array of waves, which is spread out according to the increasing or decreasing order
of wavelength or frequency.

ATOMIC SPECTRUM: It is the spectrum produced when an atom of an element absorbs energy . When an atom of
an element is supplied with energy it absorbs this energy and gets excited. The excited atom emits radiation which
when passed through a prism, is resolved into its individual components. This pattern of different components of the
radiation is called atomic spectrum. It consists of a large number of closely spaced lines, with dark space between
them. Hence it is called line spectrum.

EMISSION SPECTRUM OF HYDROGEN:

An electric discharge passed through hydrogen gas at low pressure emits a pink coloured glow. A
narrow beam of this radiation when passed through a prism, line spectrum consisting of several sharp lines is
obtained. This is because when energy is supplied to hydrogen gas, different atoms absorb different amounts of
energy. Depending on the amount of energy absorbed electrons jump to different energy levels. During each
transition, energy is released in the form of a radiation with a particular frequency. The line spectrum corresponding
to this is known as absorption spectrum.

Slit

Prism

Line spectrum
of Hydrogen
Discharge tube containing Screen
Hydrogen

The atoms in the excited state i.e., atoms after absorbing the energy are unstable. Therefore the
electros jump back to different lower energy levels in one or several steps by giving out energy in the form of
radiation. The line spectrum corresponding to this is known emission spectrum.

The spectral lines are grouped into five, namely (1) Lyman series (uv region), (2) Balmer series (visible region),
(3) Paschen series, (4) Brackett series and (5) Pfund series. Series (3), (4) and (5) in the infrared region.
The wavelength of any spectral line in any series is calculated using the formula.

υ = 1 = R 1 - 1
λ n12n22

where, υ = Wave number λ = Wavelength of the radiation, R = Rydberg’s constant = 10967758 m -1,n1 and n2
are integers, and n2>n1.
Values of n1 and n2 for various series are:

Spectral lines Value of n1 Value of n2 Spectral region

Lyman series 1 2,3,4, . . . . Ultraviolet.

Balmer series 2 3,4,5, . . . . Visible region.
Paschen series 3 4,5,6, . . . . Infrared.
Brackett series 4 5,6,7, . . . . Infrared.
Pfund series 5 6,7,8, . . . . Infrared.
Atomic Structure rbdr 11

BOHR’S THEORY OF AN ATOM:

1. Electrons revolve around the nucleus in certain fixed paths called orbits.
2. Each orbit is associated with a definite amount of energy. Hence orbits are known as energy levels.
3. Farther the energy level from the nucleus, larger is the energy associated with it.
4. As long as the electrons are in the their specific orbits, there is no energy change.
5. Energy change takes place only when electrons jump from one level to another.
When an electron falls down to a lower energy level, energy is liberated and when an electron jumps to a
higher energy level, energy is absorbed. If E2 andE1 are the energies associated with two energy levels,
where E2 > E1, Then the energy change associated with their levels is give as :

ΔE = E2 - E1 = h υ

h = Planck’s constant, υ = frequency of the radiation.

6. The angular momentum of an electron is quantised. It is a whole number multiple of h/2π
Angular momentum, mvr = nh/2π
where ‘n’ is an integer like 1,2,3, etc.

EXPLANATION OF HYDROGEN SPECTRUM USING BOHR’S THEORY:

Bohr’s theory readily explains the various lines in the hydrogen spectrum. When an atom absorbs energy
the electron moves into one of the higher energy orbits. This depends on the quantum of energy absorbed. The
electrons in the ‘excited state’ remain for a short time and then jump back to lower energy levels by emitting excess
energy as electromagnetic radiation, which corresponds to a particular frequency or wavelength.

5
Energy level Pfund series
4
Brackett series
3
Paschen series
2
Balmer series
1
Lyman series
Emission spectrum of Hydrogen

The various series present in the spectrum of hydrogen can be explained as given below:

1. Lyman series: Lyman series is obtained when the excited electron returns from any higher energy level to
the first energy level i.e., n1 = 1.Thus for spectral lines present in the Lyman series n1 =1 and n2 = 2,3,4, . . They
appear in the ultra-violet region of the spectrum. The wave number of the emitted radiation can be calculated
using the expression:
υ = 1 = R 1 - 1
λ 12 n22
2. Balmer series: Balmer series is obtained when the excited electron returns from any higher energy level to
the second energy level i.e., n1 = 2. Thus for spectral lines present in the Balmer series n1 =2and n2 = 3,4,5, . .
Atomic Structure 12
They appear in the visible region of the spectrum. The wave number of the emitted radiation can be
calculated using the expression:
υ = 1 = R 1 - 1
λ 22 n22

3. Paschen series: Paschen series is obtained when the excited electron returns from any higher energy level
to the third energy level i.e., n1 = 3. Thus for spectral lines present in the Paschen series n 1 =3 and n2 = 4,5,6, .
They appear in the infrared region of the spectrum. The wave number of the emitted radiation can be calculated
using the expression:
υ = 1 = R 1 - 1
λ 32 n22

4. Brackett series: Brackett series is obtained when the excited electron returns from any higher energy level
to the fourth energy level i.e., n1 = 4. Thus for spectral lines present in the Brackett series n 1 = 4 and n2 = 5,6,7,.
They appear in the infrared region of the spectrum. The wave number of the emitted radiation can be calculated
using the expression:
υ = 1 = R 1 - 1
λ 42 n22

MERITS OF BOHR’S THEORY:

1. It explains the hydrogen spectrum.
2. It explains the spectra of hydrogen-like uni-electron species like He+, Li+2, Be+3, etc.
3. The experimental value of Rydberg’s constant is in agreement with the value calculated by Bohr’s theory.
4. The radii and energy of orbits in hydrogen calculated experimentally is in agreement with the values
calculated using Bohr’s theory.

DEMERITS OF BOHR’S THEORY:

1. It failed to explain the spectra of multi-electron atoms.
2. It failed to explain the fine spectra of atoms.
3. It failed to explain the splitting of spectral lines in presence of electric field and magnetic field.
4. It is unable to explain the formation of bonds between atoms.
5. It conflicts with Heisenberg’s uncertainty principle.
6. It explains the stability of an atom. According to Bohr’s theory as long as the electron moves in its orbit it
does not lose energy. Thus there is no spiraling of electron into the nucleus. Thus an atom is stable.

DUAL NATURE OF ELECTRON:

The property of electron indicates that it has a dual nature i.e., it has particle and wave nature. An electron has
mass and possesses kinetic energy. Hence it behaves like a particle. Electrons can be diffracted in the same way
as light waves get diffracted. Thus it behaves like a wave.
Louis de Broglie suggested that any particle, which possesses mass and velocity, can behave as both particle
and wave. However, the wave property is insignificant for large objects. Thus a moving electron has both particle
and wave nature. This is called dual nature.

DISTINCTION BETWEEN PARTICLE AND WAVE:

Wave Particle
1. It is delocalised in space. 1. It is localised in space.
2. Its energy is calculated by its amplitude. 2. Its energy depends on its mass and
3. Two or more waves can simultaneously exist velocity.
in a given region of space. 3. Two or more particles cannot
4. Two waves in the same region may interfere simultaneously exist in a given region of
with each other. Their effects may add up or space.
Atomic Structure rbdr 13
get nullified. 4. Particles do not show interference.

de Broglie’s equation: ( Matter-Wave equation)

The de Broglie’s equation can be derived using Einstein’s equation and Planck’s equation.
Einstein’s mass- energy relationship is given as:
E = mc2 (1)
where ‘c’ is the velocity of light.
According to Planck’s equation: E=hυ (2)
where ‘υ’ is the frequency of the wave.
Equating (1) and (2) mc2 = h υ
mc2 = h c Since, υ = c
λ λ
or λ = h
mc
This is called de Broglie’s equation.
Since ‘mc’ represents the momentum the de Broglie’s equation can also be written as:
λ = h
p
where ‘p’ is the momentum of the electron.

HEISENBERG’S UNCERTAINTY PRINCIPLE: “ It is impossible to measure simultaneously the position and

momentum of an electron or any microscopic moving particle exactly”.
Mathematically it is given as,
Δx . Δp ≥ h
4π

where Δx is the uncertainty regarding position and Δp is the uncertainty regarding momentum.

QUANTUM NUMBERS:
They are numbers, which fully describe the position and energy of an electron in an atom. They are four
types namely, 1) Principal quantum number, 2) Azimuthal quantum number, 3) Magnetic quantum number and
4) Spin quantum number

1. Principal quantum number (n): It gives the main energy level or shell in which the electron is present, thus
giving the energy of an electron. It (n) can take integral values like 1,2,3 . . .etc. for which the corresponding
shells are called K, L, M . . .. respectively. The maximum number of electrons in a shell is given by 2n2, where
n is the principal quantum number.

2. Azimuthal quantum number (l) : It gives the sub-shell in which the electron is present or the angular
momentum of electron around the nucleus. It (l) takes value from 0, 1, 2, 3, . .up to (n-1).
eg. If n = 1, l = 0 ( ‘s’ sub-shell.
If n = 2, l = 0,1. ( ‘s’ and ‘p’ sub- shell respectively.
If n = 3 l = 0, 1, 2. ( ‘s’, ‘p’ and ‘d’ sub-shell respectively.
If n = 4, l = 0, 1, 2, 3, ( ‘s’, ‘p’, ‘d’ and ‘f’ sub-shell respectively.

3. Magnetic quantum number (m) : It gives the orientation of orbitals in space. Its value ranges from
- l, . . .0 . . .+ l.
eg. If l = 0, m = 0  One orientation for ‘s’ orbital.
If l = 1, m = -1, 0, +1  Three orientations for ‘p’ orbitals, px, py and pz
Atomic Structure 14
If l = 2, m = -2, -1, 0, +1, +2  Five orientations for ‘d’ orbitals, dx-y, dy-z, dx-z, dx2-y2, dz2
4. Spin quantum number (s) : It gives the spin of the electron along its own axis. The electron can rotate in
clockwise direction (↑) or anti-clock wise (↓) direction which are represented by +½ and -½ respectively. Thus
spin quantum can have two values only.

SHAPES OF ORBITALS:

Orbital: It is the space around the nucleus of an atom where there is maximum probability of finding an electron.
The spatial distribution of electron cloud decides the shape of the orbital. The electron cloud may not be
uniform density everywhere in the orbital. In an orbital there may be regions of higher probability where electron
cloud is dense and there may also be regions of low probability where electron cloud is not dense. At certain points
or planes in an orbital may also have zero probability of finding electron. Such points or planes are called nodal
points or nodal planes respectively.

Y
Y Y

X X X

Z
px py
‘s’ orbital (spherical) ‘p’ orbitals (dumb- bell)

X Y Z

Y X Y

Z py dx-y dy-z

‘d’ orbitals (double dumb bell)

Z Y Z

X X X

dx-z dx2-y2 dZ2

Atomic Structure rbdr 15
DIFERENCE BETWEEN ORBIT AND ORBITAL:

ORBIT ORBITAL
1. It is a definite circular path around the 1. It is a three dimensional region around the
nucleus of an atom in which the electron nucleus of an atom where the probability of
revolves. finding an electron is maximum.
2. It indicates the exact position of an 2. It does not specify the exact position of an
electron in an atom. electron, as an electron is treated as a
wave.
3. It represents the two dimensional (planar) 3. It represents the three dimensional motion
motion of an electron. of an electron.
4. It can accommodate a maximum of 2n2 4. It can accommodate a maximum of 2
electrons. electrons.
5. Orbits are circular in shape. 5. Orbitals have different shapes i.e.,
spherical, dumb-bell, double dumb-bell.

PAULI’S EXCLUSION PRINCIPLE: “ No two electrons in an atom can have all the four quantum numbers same”.
e.g. 2He = 1s2
Quantum numbers for the first electron of He: n = 1, l= 0, m = 0, s = +½.
Quantum numbers for the second electron of He: n = 1, l= 0, m = 0, s = -½.

AUFBAU’S PRINCIPLE: “Electrons get added in different orbitals in the order of increasing orbital energy ”.

Aufbau’s energy level diagram:

1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d 5f

6s 6p 6d 6f

Electron configuration of atoms that violate Aufbau’s principle:

24 Cr = 1s2 2s2 2p6 3s2 3p6 4s1 3d5.

Cu = 1s2 2s2 2p6 3s2 3p6 4s1 3d10.
29

42 Mo = 1s2 2s2 2p6 3s2 3p6 4s2 3d104p6 5s1 4d5.

46 Pd = 1s2 2s2 2p6 3s2 3p6 4s2 3d104p6 5s0 4d10.
This discrepancy in the above elements is attributed to the extra stability they get
because of half-filled and fully filled sub-shells.
Atomic Structure 16

General electronic configuration of s, p, d and f block elements:

1. General electronic configuration of ‘s’ block elements: ns1-2.

2. General electronic configuration of ‘p’ block elements: ns2 np1-6.
3. General electronic configuration of ‘d’ block elements: (n-1) d1-10 ns1-2.
4. General electronic configuration of ‘f’ block elements: (n-2) f1-14 (n-1)d0-1 ns2.
(n + l) RULE: It helps in comparing the energies of two atomic orbitals.

Rule (1): Between two orbitals, the orbital with lower value of (n + l), is of lower energy.

e.g. : Considering 4p and 3s orbitals.

For 4p orbital (n + l) = 4 + 1 = 5.
For 3s orbital (n + l) = 3 + 0 = 4.
Since the (n + l) value of 3s orbital is lesser than that of 4p orbital, the 3p orbital has lower
energy than 4s orbital.

Rule (2): If the values of (n + l) are same, the orbital having a higher value of ‘n’ has more energy.

e.g. : Considering 3p and 4s oritals.

For 3p orbital (n + l) = 3 + 1 = 4.
For 4s orbital (n + l) = 4 + 0 = 4.
In the above case the value of (n + l) is same for both the orbitals but the ‘n’ value of 4s
orbital is more than the ‘n’ value of 3s and hence, the4s orbital has more energy than 3p
orbital.

HUND’S RULE OFMAXIMUM MULTIPLICITY: It states that, “Pairing of electrons takes place only after each orbital
of a particular sub shell has one electron each”.

e.g. : 8O = 1s2 2s2 2p4

1s 2s 2p
↑↓ ↑ ↓ ↑↓ ↑ ↑

In oxygen atom the first two electrons enter 1s orbital and the next two electrons enter the 2s
orbital. Among the remaining four electrons, each of the 2p orbitals, Px, Py and Pz, get one electron and finally
the remaining one electron then enters the Px orbital.