Atoms

Thomson’s model of atom:

1. Every atom consists of a positively charged sphere of radius of the order of 10 -10m in
which entire mass and +ve charge of the atom are uniformly distributed.
2. Inside this sphere electrons are embedded like seeds in water melon or like plums in
a pudding.
3. The no of electrons is such that their negative charge is equal to the +ve charge of
atom. The atom is electrically neutral.

Limitations:

1. It could not explain the origin of spectral series of hydrogen and other atoms
observed experimentally.
2. It could not explain large angle scattering of -particles from thin metal foils as
observed by Rutherford.

Rutherford’s Experiment:

A radioactive source of -particles Bismuth 214 83𝐵𝑖 is taken in a lead box provided with a
narrow opening. The -particles are collimated into a narrow beam by passing them
through a narrow slit. The -particles are allowed to fall on the thin gold foil of thickness 2.1
× 10-7 m. The -particles scattered in different directions are observed with the help of
rotatable detector which consists of a zinc sulphide screen and a microscope. The scatter -
particles on striking the screen produce brief light flashes or scintillations.

Observations:

1. It is seen that most of the -particles passed straight through the foil or suffer very
small deflection.
2. Few -particles (about 1 in 8000) get deflected through 90° or more.
3. Occasionally an -particles get rebounded from the gold foil suffering a deflection of
about 180°.
Significance of the Result:-

Rutherford concluded that

1. As most of the -particles passed straight through the foil so most of the space
within the atom must be empty.
2. To explain large angle scattering of -particles, Rutherford suggested that all the +ve
charge and mass of the atom is concentrated in a very small region called nucleus of
an atom.
3. The nucleus is surrounded by a cloud of electrons whose total –ve charge is equal to
the +ve charge on the nucleus so that the atom as a whole is electrically neutral.

Graph between Scattering Angle and No. of -particles

The dots in this graph represent the data points of the actual experiment. The solid curved
line is the theoretical prediction based on the assumptions that atom has a small dense
+vely charged nucleus. An -particle carries 2units of +ve charge and has mass of a helium
atom. The charge of gold nucleus is Ze, where Z is the atomic number of atom. For gold z=79
since nucleus of gold is 50 times heavier than an -particle, it is assumed that it would
remain stationary in scattering experiment where R is the distance between -particle and
screen.

1 (2𝑒)(𝑍𝑒)
𝐹=
4𝜋𝜖0 𝑅2

Where R is the distance between the -particle and screen.

Distance of closest approach (size of a nucleus)

nucleus

-particle

r0
Consider an -particle of mass m and initial velocity v moving towards the centre of the
nucleus. As it approaches the nucleus, it experiences columbic repulsion and its kinetic
energy gets converted to potential energy. At a distance of r0 from the nucleus the -
particle stop for a moment and then begins to retrace its path. At a distance of closest
approach r0 initial K.E. of -particle = Potential energy of -particle.

1 𝑞1 𝑞2
𝑚𝑣 2 =
2 4𝜋𝜖0 𝑟

1 (2𝑒)(𝑍𝑒)
𝑚𝑣 2 =
2 4𝜋𝜖0 𝑟0

(2𝑒)(𝑍𝑒)
𝑟0 =
1
4𝜋𝜖0 (2 𝑚𝑣 2 )

-Particle Trajectory (Impact Parameter):

Impact parameter is defined as ⊥ distance of initial velocity vector of -particles from the
central line of the nucleus, the trajectory of -particle depends upon the impact parameter
(b) of collision. For large impact parameter force experienced by -particle is weak because
F varies as 1⁄𝑑2 . Therefore, when impact parameter is large -particles deviates by small
angle. In case of head on collision the impact parameter is minimum and -particle
rebounds back. If impact parameter is large  is small.

(Postulates) Rutherford’s model of atom:

1. Every atom consists of a small central core called the nucleus in which the entire +ve
charge and almost entire mass of the atom is concentrated.
2. The size of the nucleus (10-13 m) is very small as compared to the size of the atom
(10-10 m).
3. The nucleus is surrounded by a suitable by a suitable number of electrons. As an
atom on the whole is neutral, no of electrons surrounding the nucleus is equal to no
of +ve charge on nucleus.
4. These electrons revolve around the nucleus in various circular orbits as do the
planets around the sun. The centripetal force required by electrons for revolution is
provided by electrostatic force between electron and nucleus.

Limitations:

1. Electrons are continuously accelerated towards the nucleus. Accelerated charges

radiate energy. If these electrons radiate energy, the radius of their path will
decrease; the electrons will follow a spiral path and ultimately fall into the nucleus.
Rutherford could not explain the stability of atom.
 2. In Rutherford’s model an electron can revolve in orbits of all possible radii, it should
emit a continuous spectrum but experimentally the atomic spectra are found to be
discrete.

Electron Orbits:

The electrostatic force of attraction (Fe) between the revolving electrons and nucleus
provides the centripetal force (Fc) to keep them in their orbits for a dynamically stable orbit
in hydrogen orbit,

𝐹𝑐 = 𝐹𝑒

𝑚𝑣 2 𝑒2
=
𝑟 4𝜋𝜖𝑜 𝑟 2

𝑒2
𝑟=
4𝜋𝜖0 𝑚𝑣 2

Kinetic energy of electron in orbit

1
𝐾 = 2 mv2

𝑒2
𝐾=
8𝜖0 𝑟

Potential energy of electron in orbit

(𝑒)(−𝑒)
𝑈=
4𝜋𝜖0 𝑟

-ve sign indicates that electrons are bound to the nucleus (+ve) by electrostatic forces.

Total energy of electron in hydrogen atom

𝑒2 𝑒2
𝐸= −
8𝜋𝜖0 𝑟 4𝜋𝜖0 𝑟

−𝑒 2
𝐸=
8𝜋𝜖0 𝑟

Atomic Spectra

1. Line Emission Spectrum:- when an atomic gas or vapour at low pressure is excited by
passing an electric current through it, the emitted radiation has a spectrum which
contains certain specific wavelengths only this kind of spectrum is called line
emission spectrum and it consists of a few bright lines on a dark background.
 2. Line Absorption Spectrum:- When the white light is passed through the same gas or
vapours, we observe a bright background crossed by a few bright lines signifying the
wavelengths that are absorbed by the gas. They form the line absorption spectrum.

Spectral Series:- Hydrogen is the simplest atom and has the simplest spectrum. In the
observed spectrum, the spacing between the lines within certain sets of hydrogen spectrum
increase in a regular way. Each of these sets is called spectral series.

Emission lines in the spectrum of hydrogen

Balmer was the first to observe one such spectrum. It is called Balmer series.

1. The spectral line with largest wavelength, 656nm is the red region called H line.
2. The next line with =486.1nm in the blue green region is called H line.
3. The next line with =434.1nm is in violet region is called the Hy line and so on.

As the wavelength decreases, the lines appear closer together and are weaker in intensity.

Ballmer found an empirical formula for the observed wavelengths

1 1 1
𝜗̅ =  = 𝑅(22 − 𝑛2 )

R= 1.097×107 m-1 and is called Rydberg constant where n=3,4,5,-------

For n=3

1 1 1
= 1.097 × 107 ( 2 − 2 )
𝜆 2 3

1
= 1.522 × 106 𝑚−1
𝜆
𝜆 = 656.3𝑛𝑚 Which is the wavelength of the H line.

Similarly for n=4, 𝜆 = 486.1𝑛𝑚

For n= 𝜆 = 364.6𝑛𝑚 which is the limit of Balmer series

Beyond this limit there are no further distinct lines instead the spectrum becomes
continuous though faint. Later on other series of spectra for hydrogen were discovered and
these are known as Layman, Balmer, Paschen, Brackett and Pfund.

Lyman Series:

It was discovered in the U.V. region of hydrogen spectrum.

1 1 1
= 𝑅(12 − 𝑛2 ), where n=2,3,----------
𝜆

Paschen Series:

It was discovered in the infrared region of the hydrogen spectrum.

1 1 1
= 𝑅(32 − 𝑛2 ), where n=4,5,------------
𝜆

Brackett Series: it was discovered in the infrared region of hydrogen spectrum.

1 1 1
= 𝑅(42 − 𝑛2 ), where n=5,6,------------
𝜆

Pfund Series:

It was discovered in the infrared region of the hydrogen spectrum

1 1 1
= 𝑅(52 − 𝑛2 ) , where n=6,7,---------
𝜆

Bohr’s Model of Hydrogen Atom:

Bohr combines classical ideas and early quantum concepts to give what is known as Bohr
model of hydrogen atom.

Postulates of Bohr Theory of Hydrogen Atom:

1. Nuclear Concept: This postulates stresses that an electron in an atom can revolve in
certain stable orbits only without the emission of radiant energy. These are called
stationary states of the atom. The centripetal force required for their rotation is
provided by the electrostatic attraction between electron and the nucleus.
𝑚𝑣 2
𝐹𝑐 =
𝑟
(𝑍𝑒)(𝑒)
𝐹𝑒 =
4𝜋𝜖0 𝑟 2
 [for hydrogen Z=1]

𝑚𝑣 2 (𝑍𝑒)(𝑒)
=
𝑟 4𝜋𝜖0 𝑟 2

2. Quantum Condition: Electron can revolve only in certain discrete non radiating
orbits called stationary orbits for which total angular momentum of the revolving
ℎ
electron is an integral multiple of , where h is planks constant. Thus angular
2𝜋
momentum of the orbiting electron is quantised.
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
−
Where angular momentum of orbiting 𝑒 = 𝑚𝑣𝑟
3. Stationary Orbits: while revolving in the permissible orbits, an electron does not
radiate energy. These non-radiating orbits are called stationary orbits.
4. Frequency Condition: An atom emits or absorbs radiation in the form of discrete
photons when an electron jumps from higher to lower orbit or lower to higher orbit.
If E1 is the total energy of electron in stationary orbit and E2 is the total energy in the
outer stationary orbit, then frequency of radiation emitted on jumping from outer to
inner orbit is given by
𝐸 = 𝐸2 − 𝐸1 = ℎ𝑣
5. Radii of Bohr’s Stationary Orbit:
From second postulate
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
𝑛ℎ
𝑣=
2𝜋𝑚𝑟
From first postulate
𝑚𝑣 2 𝐾𝑍𝑒 2
= 2
𝑟 𝑟
𝑚𝑛2 ℎ2 𝐾𝑍𝑒 2
= 2
𝑟 3 4𝜋 2 𝑚2 𝑟
𝑛2 ℎ2
𝑟= 2
4𝜋 𝑚𝐾𝑍𝑒 2
𝑟 ∝ 𝑛2

Radii of stationary orbits are in the ratio 1:4:9 and so on

h=6.626×10-34 Js, m=6.1×10-31Kg, K=9×109 Nm2C-2, e=1.6×10-19C
𝑟 = 𝑛2 × 5.29 × 10−11 𝑚
Size of first orbit
𝑟 = 12 × 5.29 × 10−11 𝑚
r=0.529Å
Velocity of Electron in Bohr’s Stationary Orbit:

From 1st postulate

𝑚𝑣 2 𝐾𝑍𝑒 2
= 2
𝑟 𝑟
𝐾𝑍𝑒 2
𝑟=
𝑚𝑣 2
From IInd postulate

𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
𝑛ℎ
𝑟=
2𝜋𝑚𝑣
From 1 and 2

𝐾𝑍𝑒 2 𝑛ℎ
=
𝑚𝑣 2 2𝜋𝑚𝑣
2𝜋𝐾𝑍𝑒 2
𝑣=
𝑛ℎ
2.2 × 106
𝑣=
𝑛
For n=1, v=2x106m/s = c/137

Frequency of Electron in Bohr’s Stationary Orbit:

It is the number of revolutions completed per second by the electron in a stationary orbit
around the nucleus.

𝑣 = 𝑟𝜔

𝜔 = 2𝜋𝜗

𝑣 = 2𝜋𝜗𝑟
𝑣
𝜗=
2𝜋𝑟
2𝜋𝐾𝑍𝑒 2
𝜗=
𝑛ℎ2𝜋𝑟
𝐾𝑍𝑒 2
𝜗=
𝑛ℎ𝑟
For 1st orbit n=1, r=0.53x10-10m, K=9x109Nm2C-2, Z=1, h=6.6x10-34J

We get, =6.57x1015rps

Total Energy of 𝒆− in Bohr Stationary Orbit: E=P.E+K.E

𝑚𝑣 2 𝐾𝑍𝑒 2
From 1st postulates =
𝑟 𝑟2

1 1 𝐾𝑍𝑒 2
K.E. of 𝑒 − = 2 𝑚𝑣 2 = 2 𝑟

𝐾𝑍𝑒
Potential due to nucleus = 𝑟

𝐾𝑍𝑒(−𝑒) 𝐾𝑍𝑒 2
P.E. of 𝑒 − = 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 × 𝑐ℎ𝑎𝑟𝑔𝑒 = =−
𝑟 𝑟

Total Energy, E=K.E.+P.E.

𝐾𝑍𝑒 2 𝐾𝑍𝑒 2 𝐾𝑍𝑒 2

𝐸= − =−
2𝑟 𝑟 2𝑟
(PE = 2 TE, KE = -TE)

𝑛2 ℎ 2
Put 𝑟 = 4𝜋2𝑛𝐾𝑍𝑒 2

2𝜋 2 𝑚𝐾 2 𝑍 2 𝑒 4
𝐸=−
𝑛2 ℎ2
For hydrogen , Z=1

21.76 × 10−19
𝐸=−
𝑛2
21.76 × 10−19
𝐸=− 𝑒𝑉
𝑛2 × 1.6 × 10−19
−13.6
𝐸= 𝑒𝑉
𝑛2
Origin of Spectral Lines:

Most of the hydrogen atom is in ground state at room temperature. When it receives
energy by processes such as electron collisions or heat. They require energy and 𝑒 − jumps
to higher energy state i.e. from n=1 to n=2,3,………. And so on. The atom is said to be in
excited state. From these states electron can fall back to a state of lower energy by emitting
photon of particular energy.

Let E1= energy of electron in n1 orbit

E2=energy of electron in n2 orbit

 ℎ𝑣 = 𝐸2 − 𝐸1

−2𝜋 2 𝑚𝐾 2 𝑍 2 𝑒 4 2𝜋 2 𝑚𝐾 2 𝑍 2 𝑒 4
ℎ𝑣 = +
𝑛22 ℎ2 𝑛12 ℎ2

𝑐 2𝜋 2 𝑚𝐾 2 𝑍 2 𝑒 4 1 1
ℎ = ( 2 − 2)
 ℎ 2 𝑛1 𝑛2

1 2𝜋 2 𝑚𝐾 2 𝑍 2 𝑒 4 1 1
= ( 2 − 2)
 𝑐ℎ 3 𝑛1 𝑛2
1
Where  = 𝑉̅ , 𝑤𝑎𝑣𝑒 𝑛𝑜 𝑜𝑓 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛 𝑒𝑚𝑖𝑡𝑡𝑒𝑑

2𝜋 2 𝑚𝐾 2 𝑒 4
= 𝑅, 𝑅𝑦𝑑𝑏𝑒𝑟𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑐ℎ3
R=1.097x107m-1

1 1
𝑉̅ = 𝑅𝑍 2 ( 2 − 2)
𝑛1 𝑛2

For hydrogen, z=1

1 1
𝑉̅ = 𝑅( 2 − 2)
𝑛1 𝑛2

Note: - Limiting line of any spectral series n2 = infinity

Bohr’s Explanation of Spectral Series of Hydrogen Atom

1. Lyman Series: Lyman series is obtained when an electron jumps to the 1 st orbit from
any outer orbit and n2=2,3,….

1 1
𝑉̅ = 𝑅( 2 − 2)
𝑛1 𝑛2
1 1
𝑉̅ = 𝑅(1 − 𝐾2 ) where K=2,3,…..

Value of 𝑉̅ lies in the UV region of spectrum

2. Balmer Series: Balmer series is obtained when an electron jumps to the 2 nd orbit
from any outer orbit.
1 1
𝑉̅ = 𝑅( 2 − 2 ) where K=3,4,……….
2 𝐾

Value of 𝑉̅ lies in the visible part of spectrum

3. Paschen Series: Paschen series is obtained when an electron jumps to the 3 rd orbit
from any outer orbit.
 1 1
𝑉̅ = 𝑅(32 − 𝐾2 ) where K=4,5,………

Value of 𝑉̅ lies in the infrared region

4. Brackett Series: this series is obtained when an electron jumps to the 4 th orbit from
any outer orbit.
̅ = 𝑅( 1 1
𝑉 − ) where K=5,6,………
42 𝐾2
Value of 𝑉̅ lies in the infrared region
5. Pfund Series: this series is obtained when an electron jumps to the 5 th orbit from any
outer orbit.
̅ = 𝑅( 1 1
𝑉 − ) where K=6,7,………
52 𝐾2
Value of 𝑉̅ lies in the infrared region

Energy Level Diagram:

Energy level diagram is one in which energies of various stationary states of an atom are
represented by parallel horizontal lines drawn according to suitable line scale.

Energy Levels of Hydrogen:

From Bohr’s theory, total energy of an electron in nth orbit of hydrogen atom is

−13.6
𝐸𝑛 = 𝑒𝑉
𝑛2
E1=-13.6eV

−13.6
𝐸2 = 𝑒𝑉 = −3.11𝑒𝑉
4

E3=-1.51eV

E4=-0.85eV

E5=0.54eV
Debroglie Explanation of Bohr’s Second Postulates of Quantisation:

The second postulates of Bohr model of an atom says that angular momentum of 𝑒 −
orbiting around the nucleus is quantised i.e.

ℎ
𝑚𝑣𝑟 = 𝑛
2𝜋
Where n=1,2,3,………..

According to De-Broglie the electron in its circular orbit as proposed by Bohr must be
seen as a particle wave. Hence according to him, a stationary orbit is that which contains
an integral number of De-Broglie waves associated with the revolving electron.

Total distance covered =2rn

For permissible orbit 2rn=n

ℎ
Debroglie wavelength  = 𝑚𝑣
𝑛

Where 𝑣𝑛 is the speed of 𝑒 − in nth orbit

𝑛ℎ
2𝜋𝑟𝑛 =
𝑚𝑣𝑛

𝑛ℎ
𝑚𝑣𝑛 𝑟𝑛 =
2𝜋
ℎ
i.e. angular momentum of 𝑒 − revolving in nth orbit must be an integral multiple of 2𝜋
which is the quantum condt proposed by Bohr in 2nd postulate.
 A standing wave is shown in the circular orbit where 4 De-Broglie wavelengths fit into
the circumference of the orbit.

Limitation of Bohr’s Theory:

1. This theory is applicable to simplest atom like hydrogen with z=1. The theory fails in
case of atoms of other elements for which Z>1.
2. It does not explain why orbits of electrons are taken as circular while elliptical orbits
are also possible.
3. It does not explain the fine structure of spectral lines even in hydrogen atom.
4. It does not take into account the wave properties of electron.
5. It does not say anything about the relative intensities of the spectral lines.

Excitation : It is the process of absorption of energy by an electron of an atom when it

jumps from lower energy state to higher energy state.

Excitation energy: It is defined as the energy required by an electron to jump from the
ground state to any of the excited states, First excitation energy of hydrogen is

= E2 – E1 = - 3.4 - (-13.6) = 10.2 eV

Excitation potential : It is defined as the potential difference through which an electron in

an atom must be accelerated so that it may go from the ground state to the excited state.
First excitation potential of hydrogen

= - 3.4 - (-13.6) = 10.2 V

Second excitation potential of hydrogen

= -1.51 – (-13.6) = 12.09 V

Ionisation : The process of knocking out an electron from the atom is called ionization.

Ionisation energy: It is defined as the energy required to knock an electron completely out
of the atom i.e. energy required to take an electron from its ground state to the outermost
orbit (n=6). Ionisation energy of hydrogen

= 𝐸∞ − E1 = 0 – (-13.6) = 13.6 eV

Ionisation potential : The potential difference through which an electron of the atom is
accelerated so that it is knocked out of the atom. The ionization potential of hydrogen atom
= 0 – (-13.6) = 13.6 V