Physical chemistry

Class -11
lecture-2
By lok raj joshi
 Thomson’s Atomic Model
 In 1898, J. J. Thomson proposed the first of many atomic models to come. He
proposed that an atom is shaped like a sphere with a radius of approximately
10-10m, where the positive charge is uniformly distributed. The electrons are
embedded in this sphere so as to give the most stable electrostatic
arrangement.
 This model is also referred to as the watermelon model, the plum pudding
model or the raisin pudding model because its resemblance withcut
watermelon with seeds inside or it as a pudding with the electrons being the
plum or the raisins in the pudding.
 An important aspect of this model is that it assumes that the mass of the
atom is uniformly distributed over the atom.
 Thomson’s atomic model was successful in explaining the overall neutrality of
the atom. However, its propositions were not consistent with the results of
later experiments.

Figure: Thompson’s water melon model

 Rutherford’s Atomic model
Rutherford’s α-scattering experiment:
 Rutherford’s conducted an experiment by bombarding a thin sheet of gold
with α-particles and then studied the trajectory of these particles after their
interaction with the gold foil.
 Rutherford, in his experiment, directed high energy streams of α-particles
from a radioactive source at a thin sheet (100 nm thickness) of gold. In order
to study the deflection caused to the α-particles, he placed a zinc sulphide
screen around the thin gold foil. Rutherford made certain observations that
contradicted Thomson’s atomic model.
Observations of Rutherford’s Alpha Scattering Experiment
The observations made by Rutherford led him to conclude that:
 A major fraction of the α-particles bombarded towards the gold sheet passed
through it without any deflection, and hence most of the space in an atom is
empty.
 Some of the α-particles were deflected by the gold sheet by very small
angles, and hence the positive charge in an atom is not uniformly
distributed. The positive charge in an atom is concentrated in a very small
volume.
 Very few of the α-particles were deflected back, that is only a few α-particles
had nearly 1800 angle of deflection. So the volume occupied by the positively
charged particles in an atom is very small as compared to the total volume of
an atom.
Conclusions
 Based on the above observations and conclusions, Rutherford proposed the
atomic structure of elements. According to the Rutherford atomic model:
 The positively charged particles and most of the mass of an atom was
concentrated in an extremely small volume. He called this region of the atom
as a nucleus.
 Rutherford model proposed that the negatively charged electrons surround the
nucleus of an atom. He also claimed that the electrons surrounding the nucleus
revolve around it with very high speed in circular paths. He named these
circular paths as orbits.
 Electrons being negatively charged and nucleus being a densely concentrated
mass of positively charged particles are held together by a strong electrostatic
force of attraction.

Limitations of Rutherford Atomic Model:

Although the Rutherford atomic model was based on experimental observations it
failed to explain certain things:
 Rutherford proposed that the electrons revolve around the nucleus in fixed
paths called orbits. According to Maxwell, accelerated charged particles emit
electromagnetic radiations and hence an electron revolving around the nucleus
should emit electromagnetic radiation. This radiation would carry energy from
the motion of the electron which would come at the cost of shrinking of orbits.
Ultimately the electrons would collapse in the nucleus. Calculations have shown
that as per the Rutherford model, an electron would collapse in the nucleus in
less than 10-8 seconds. So Rutherford model was not in accordance with
Maxwell’s theory and could not explain the stability of an atom.
 One of the drawbacks of the Rutherford model was also that he did not say
anything about the arrangement of electrons in an atom which made his
theory incomplete.
 Although the early atomic models were inaccurate and failed to explain
certain experimental results, they were the base for future developments in
the world of quantum mechanics.
 Bohr’s atomic model
Introduction to the Bohr Model
 Bohr model of the atom was proposed by Neil Bohr in 1915. It came into
existence with the modification of Rutherford’s model of an atom.
Rutherford’s model introduced the nuclear model of an atom, in which he
explained that a nucleus (positively charged) is surrounded by negatively
charged electrons.
 Bohr modified this atomic structure model by explaining that electrons move
in fixed orbitals (shells) and not anywhere in between and he also explained
that each orbit (shell) has a fixed energy level.
 Rutherford basically explained the nucleus of an atom and Bohr modified that
model into electrons and their energy levels.
Postulates of Bohr’s theory:
1. Stationary states
The electrons in an atom revolve around the nucleus in a fixed circular path
called orbit. An electron in a particular orbit has a fixed amount of energy and as
long as electron revolves in fixed energy level, atom neither emits nor absorbs
radiation. Such orbits are called stationary states.

Electrons not
permitted here

Figure: Stationary energy levels in an atom

2. Quantization of radiant energy of atomic system
a. An atom neither emits nor absorbs energy when it is in particular orbit.
Energy is emitted or absorbed in the form of discrete packets of
energy called quantum only when electron jumps from one energy
level to another.
b. Energy is absorbed when electron jumps from lower to higher orbit
and energy is released when electron jumps from higher to lower
orbit. Atom with electron in higher energy level is called excited state
atom and the atom with electron in lower energy level is called ground
state atom.
c. The magnitude of energy emitted or absorbed by an atom is equal to the
difference of energy between two energy levels which is equal to discrete
quantity hv .
i.e ΔE = E2-E1= hv
Where h= 6.626 x 10-34Js
v= frequency of radiation
Farther the energy levels from the nucleus higher will be energy associated
with it, so E2 > E1.
3. Quantization of angular momentum
Only those selected orbits are permissible in which the angular momentum
of an electron is the integral multiple of h/2π
ie mvr = nh/2π
Where, m= mass of electron
v= velocity of the electron
r= radius of atom
h= Planck’s constant
n= number representing the orbit , called principle quantum number
which is positive whole number (n=1,2,3…)
4. Stability of an atom
Electrons in a given stationary state is assumed to move around the
stationary nucleus in such a way that it produces centrifugal force that
counterbalances the electrostatic force of attraction between the nucleus
and the electron.
On the basis of these assumption Bohr calculated the radius of orbit of
hydrogen atom, energy associated with each orbit and the wavelength of the
radiation emitted and the wavelengths calculated were found to be in
agreement with actual spectrum of hydrogen.
Success of Bohr’s theory
 This theory explains the stability of an atom
 This theory explains successfully the atomic spectrum of hydrogen atom
 Energy and the radius of the nth orbit of a mono-electronic system H, Li++ can
be calculated
 Origin of Hydrogen spectrum
 We all know that electrons in an atom or a molecule absorb energy and get
excited, they jump from a lower energy level to a higher energy level, and they
emit radiation when they come back to their original states. This phenomenon
accounts for the emission spectrum through hydrogen too, better known as the
hydrogen emission spectrum.
 In the late 1800s, it was known that when a gas is excited using an electric
discharge and the light emitted is viewed through a diffraction grating; the
spectrum observed consists not of a continuous band of light, but of individual
lines with well-defined wavelengths. Experiments have shown that the
wavelengths of the lines were characteristic of the chemical element emitting the
light. They were an atomic fingerprint which resulted from the internal structure
of the atom.
 The hydrogen spectrum is an important piece of evidence to show the quantized
electronic structure of an atom. The hydrogen atoms of the molecule dissociate as
soon as an electric discharge is passed through a gaseous hydrogen molecule. It
results in the emission of electromagnetic radiation initiated by the energetically
excited hydrogen atoms. The hydrogen emission spectrum comprises radiation of
discrete frequencies. These series of radiation are named after the scientists who
discovered them.
The Hydrogen spectrum
 In 1914, Niels Bohr proposed a theory of the hydrogen atom which explained
the origin of its spectrum and which also led to an entirely new concept of
atomic structure. According to this theory, the wavelengths of the hydrogen
spectrum could be calculated by the following formula known as the Rydberg
formula:

Where, λ is the wavelength of the light emitted in vacuum in units of cm,

RH is the Rydberg constant for hydrogen (109,677.581 cm-1),
nl = lower energy state and nh = higher energy state ,such that nl < nh
 There are now at least five different spectral series for hydrogen atom in
different regions of electromagnetic waves and Bohr’s theory can be used to
explain the origin of each of the spectral series as follows:
 Lyman series (nl=1)
 The series was discovered during the years 1906-1914, by Theodore Lyman.
Thus it is named after him. According to Bohr’s model, Lyman series is
displayed when electron transition takes place from higher energy
states(nh=2,3,4,5,6,…) to nl=1 energy state. All the wavelength of Lyman
series falls in Ultraviolet band.

1 1 1
V= = RH - 2
λ 1 2 nh

Balmer series (nl=2)

 The series was discovered during the years 1885, by Johann Balmer. Thus the
series is named after him. Balmer series is displayed when electron transition
takes place from higher energy states(nh=3,4,5,6,7,…) to nl=2 energy state.
All the wavelength of Balmer series falls in visible part of electromagnetic
spectrum(400nm to 740nm).

1 1 1
V= = RH - 2
λ 2 2 nh
 Paschen series (nl=3)
 The series was first observed during the years 1908, by a German physicist
Friedrich Paschen. Thus the series is named after him. Paschen series is
displayed when electron transition takes place from higher energy
states(nh=4,5,6,7,8,…) to nl=3 energy state. All the wavelength of Paschen
series falls in the Infrared region of the electromagnetic spectrum. The
shortest wavelength of next series, i.e., Brackett series overlap with Paschen
series.
Brackett series (nl=4)
 The series was first observed during the years 1922, by an American physicist
Friedrich Sumner Brackett. Thus the series is named after him. Brackett
series is displayed when electron transition takes place from higher energy
states(nh=5,6,7,8,9…) to nl=4 energy state. All the wavelength of Brackett
series falls in Infrared region of the electromagnetic spectrum.
Pfund series (nl=5)
 The series was first observed during the years 1924, by August Harman Pfund.
Thus, the series is named after him. Pfund series is displayed when electron
transition takes place from higher energy states(nh=6,7,8,9,10,…) to nl=5
energy state. All the wavelength of Pfund series falls in Infrared region of the
electromagnetic spectrum.
Figure: Illustration of different spectral predicted by Bohr’s
model
Limitations of Bohr’s theory :
(i) It does not explain the spectra of atoms having more than one electron.

(ii) Bohr’s atomic model failed to account for the effect of the magnetic field
(Zeeman Effect) or electric field (Stark effect) on the spectra of atoms or ions.
It was observed that when the source of a spectrum is placed in a strong
magnetic or electric field, each spectral line further splits into a number of
lines. This observation could not be explained on the basis of Bohr’s model.

(iii) De Broglie suggested that electrons like light have a dual character. It has
particle and wave characters. Bohr treated the electron only as particles.

(iv) Another objection to Bohr’s theory came from Heisenberg’s Uncertainty

Principle. According to this principle “It is impossible to determine
simultaneously the exact position and momentum of a small moving particle
like an electron”. The postulate of Bohr, that electrons revolve in well-defined
orbits around the nucleus with well-defined velocities is thus not tenable.
 Bohr–Bury rules of electronic configuration:
Bohr and Bury simultaneously proposed the
following rules for the distribution of electrons
in different shells.
 Rule 1: The maximum number of electrons that
can be accommodated in a shell is equal to 2n2
where ‘n’ is the quantum number of the shell
(i.e., the serial number of the shell from the
nucleus).
 Rule 2: The maximum number of electrons that
can be occupied in an outermost orbit is 8.
 Rule 3: electrons are not accommodate in a
given shell, unless the inner shells are filled.
That is, the shell are filled in a step wish
manner.