ATOMS

Chapter 12
 Introduction
• The structure of matter that shapes the world around us has been a subject of
study since long time
• The first contribution in this regard came from Dalton who postulated that
matter is made of atoms, which are indivisible. The word atom comes from a
Greek word A-tomos which means ‘no cut’. J.J. Thomson proposed a structure for
the atom, which was modified by Rutherford and later by Neil's Bohr.
• Dalton’s Atomic Theory All elements are consists of very small invisible particles,
called atoms. Atoms of same element are exactly same and atoms of different
element are different.
• Thomson’s Atomic Model Every atom is uniformly positive charged sphere of
radius of the order of 10-10 m, in which entire mass is uniformly distributed and
negative charged electrons are embedded randomly. The atom as a whole is
neutral. This was also known as plum-pudding model of an atom.

• Limitations of Thomson’s Atomic Model

• It could not explain the origin of spectral series of hydrogen and other atoms.
• It could not explain large angle scattering of α – particles.
 Rutherford’s α – Ray Scattering Experiment
An α – particle is helium nucleus containing 2 protons and 2 neutrons. Therefore ,
an alpha particle has 4 units of mass. This experiment was done by Rutherford and
his collaborators , Geiger and Marsden and is shown in fig.

+ Gold Atom
• Geiger and Marsden carried out few experiments on the advice of Rutherford
• they directed a beam of 5.5 MeV α-particles emitted from a 21483𝐵𝑖 radioactive source

at a thin metal foil made of gold.

• The beam was allowed to fall on a thin foil of gold of thickness 2.1 × 10−7m.
• Scattered α-particles when strike zinc-sulphide screen(surrounding the thin gold
foil) produced light flashes(scintillations) which were observed via
detector(microscope)
• The scattered alpha-particles on striking the screen produced brief light flashes or
scintillations.
• These flashes may be viewed through a microscope and the distribution of the
number of scattered particles may be studied as a function of angle of scattering.
 Observations
S. No. Observation Conclusion

1 Most of the α-particles passed straight through It indicates that most of the space in an atom is
the gold foil. empty.

2 Some of the α-particles were scattered by only α-particles being +vely charged and heavy compared
small angles, of the order of a few degrees. to electron could only be deflected by heavy and
positive region in an atom. It indicates that the
positive charges and the most of the mass of the atom
are concentrated at the center called ‘nucleus’.

3 A few α-particles (1 in 9000) were deflected α-particles which travel towards the nucleus directly
through large angles (even greater than 90°). get retarded due to Coulomb’s force of repulsion and
ultimately comes to rest and then fly off in the
Some of them even retraced their path. i.e.
opposite direction.
angle of deflection was 180°.
A typical graph of the total number of α-particles scattered at different angles, in a
given interval of time, is shown in Fig. The dots in this figure represent the data
points.
 Conclusion
• Rutherford argued that, to deflect the α-particle backwards, it must experience a
large repulsive force. This force could be provided if the greater part of the mass
of the atom and its positive charge were concentrated tightly at its centre.

• This led Rutherford to postulate that entire positive charge of the atom must be
concentrated in a tiny central core of the atom. This tiny central core of each atom
was called atomic nucleus.
 Distance of Closest Approach
Distance of closest approach is the minimum distance between α particle and
centre of nucleus just before it reflects back by 180 degree.
When the distance between α-particle and the nucleus is equal to the distance of
the closest approach (𝑟0 ), the α-particle comes to rest. At this point or distance, the
kinetic energy of α-particle is completely converted into electric potential energy of
the system.
1 1 2𝑍𝑒 2
𝑚𝑣 2 =
2 4𝜋𝜀0 𝑑
Re arranging the above equation we get
1 2𝑍𝑒 2
𝑑=
4𝜋𝜀0 𝐾. 𝐸
 Impact Parameter
The trajectory traced by an α-particle depends on the impact parameter, b of
collision. The impact parameter is the perpendicular distance of the initial
velocity vector of the α-particle from the central line of the nucleus.
For large impact parameters, force experienced by α-particle is weak as F varies
inversely as square of distance and α-particle will deviate much smaller and vice-
versa.
Rutherford calculated- u θ
2 𝜃
1 𝑍𝑒 cot 2 b
+
𝑏= r0
4𝜋𝜀0 𝐾𝐸
 Rutherford’s Model of an Atom
• An atom is composed of positively charged particles. Majority of the mass of an
atom was concentrated in a very small region. This region of the atom was called
as the nucleus of an atom. It was found out later that the very small and dense
nucleus of an atom is composed of neutrons and protons.
• Atoms nucleus is surrounded by negatively charged particles called electrons.
The electrons revolve around the nucleus in a fixed circular path at very high
speed. These fixed circular paths were termed as “orbits.”
• An atom has no net charge or they are electrically neutral because electrons are
negatively charged and the densely concentrated nucleus is positively charged. A
strong electrostatic force of attractions holds together the nucleus and electrons.
• The size of the nucleus of an atom is very small in comparison to the total size of
an atom.
 Electron Orbits
The electrostatic force of attraction, (Fe) between the revolving electrons and the
nucleus provides the requisite centripetal force (Fc) to keep them in their orbits.
Thus, for a dynamically stable orbit in a hydrogen atom,
𝐹𝑒 = 𝐹𝑐
𝑚𝑣 2 1 𝑍𝑒 2
=
𝑟 4𝜋𝜀0 𝑟 2

1 𝑍𝑒 2
𝑚𝑣 2 =
4𝜋𝜀0 𝑟
Multiplying both side with half
1 1 𝑍𝑒 2
𝑚𝑣 2 =
2 8𝜋𝜀0 𝑟
 1 𝑍𝑒 2
𝐾𝑖𝑛𝑒𝑡𝑖𝑐 𝐸𝑛𝑒𝑟𝑔𝑦 =
8𝜋𝜀0 𝑟

using the electrostatic potential between 2 charged body, we get:

1 𝑍𝑒 2
𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = −
4𝜋𝜀0 𝑟
Negative sign here shows that there is a force of attraction and energy has to be
given to the system to overcome this force of attraction
•Total Energy(T):
1 𝑍𝑒 2
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = −
8𝜋𝜀0 𝑟
 ATOMIC SPECTRA
• When an atomic gas or vapour is excited at low pressure, usually by passing
an electric current through it, the emitted radiation has a spectrum which
contains certain specific wavelengths only. A spectrum of this kind is termed
as line emission spectrum and it consists of bright lines on a dark
background.
• When white light passes through a gas and we analyze the transmitted light
using a spectrometer we find some dark lines in the spectrum. These dark
lines correspond precisely to those wavelengths which were found in the
emission line spectrum of the gas. This is called the absorption spectrum of the
material of the gas.
 Spectral Series of Hydrogen
• Hydrogen is the simplest atom and therefore, has the simplest spectrum. In
the observed spectrum, however, at first sight, there does not seem to be any
resemblance of order or regularity in spectral lines. Each of these sets is called
a spectral series. In 1885, the first such series was observed by a Swedish,
Johann Jakob Balmer (1825–1898) in the visible region of the hydrogen
spectrum. This series is called Balmer series . The line with the longest
wavelength, 656.3 nm in the red is called 𝐻𝛼 , the next line with wavelength
486.1 nm in the blue green is called 𝐻𝛽 , the third line 434.1 nm in the violet is
called 𝐻𝛾 ; and so on.
• Balmer found a simple empirical formula for the observed wavelengths
1 1 1 Where, n = 3,4,5…….
=𝑅 2− 2
λ 2 𝑛 R is a constant called the Rydberg constant 1.097 × 10−7 𝑚−1
Other series of spectra for hydrogen were subsequently discovered. These are
known, after their discoverers, as Lyman, Paschen, Brackett, and Pfund series.
These are represented by the formulae:
 Limitations of Rutherford Atomic Model
• Can’t explain Stability of atom According to classical electromagnetic theory, an
accelerating charged particle emits radiation in the form of electromagnetic waves. The
energy of an accelerating electron should therefore, continuously decrease. The electron
would spiral inward and eventually fall into the nucleus. Thus, such an atom can not
be stable.

• Can’t explain Line spectra of atom Further, according to the classical electromagnetic
theory, the frequency of the electromagnetic waves emitted by the revolving electrons is
equal to the frequency of revolution. As the electrons spiral inwards, their angular
velocities and hence their frequencies would change continuously, and so will the
frequency of the light emitted. Thus, they would emit a continuous spectrum, in
contradiction to the line spectrum actually observed.
 Bohr’s Model of an Atom
Niel's Bohr (1885 – 1962) made certain modifications in this model by adding the ideas of the
newly developing quantum hypothesis.
Postulates of Bohr’s model:-
• Every atom consist of central core called nucleus, in which entire positive charge and almost entire mass of
atom are concentrated. A suitable no. Of electrons revolve around the nucleus in circular orbits. The
centripetal force for revolution is provided by electrostatic force of attraction between electron and the
nucleus.
• Electron revolves around the nucleus only in those orbits for which the angular momentum is some integral
multiple of h/2π where h is the Planck’s constant. Thus the angular momentum (L) of the orbiting electron is
quantised. 𝑛ℎ
𝐿=
2𝜋
• An electron might make a transition from one of its specified non-radiating orbits to another of lower
energy. When it does so, a photon is emitted having energy equal to the energy difference between the initial
and final states. The frequency of the emitted photon is then given by
ℎν = 𝐸𝑖 − 𝐸𝑓
 Bohr’s Radius:
The radius on which electron move around the nucleus in the orbit described by the Bohr’s model is known
as Bohr’s radius.
Using the second postulate of Bohr’s model
𝑛ℎ
𝐴𝑛𝑔𝑢𝑙𝑎𝑟 𝑀𝑜𝑚𝑒𝑛𝑡𝑢𝑚 =
2𝜋
𝑛ℎ
𝑚𝑣𝑟 = … … … … … … … (1)
2𝜋

We can create an equation for 𝑣 2 from equation (1)

2 ℎ2
𝑛
𝑣 2 = 2 2 2 … … … … … . . (2)
4𝜋 𝑚 𝑟
We know in this case two forces are there. We equate these forces then we get

𝑚𝑣 2 𝑍𝑒 2
= From this can create an equation for 𝑣 2
𝑟 4𝜋𝜀0 𝑟 2
 𝑍𝑒 2
𝑣2 = …………. 3
4𝜋𝜀0 𝑚𝑟
Equate the two equations of 𝑣 2 we get,
𝑛2 ℎ2 𝑍𝑒 2
=
4𝜋 2 𝑚2 𝑟 2 4𝜋𝜀0 𝑚𝑟

𝑛2 ℎ2 𝑍𝑒 2
=
𝑚𝑟𝜋 𝜀0

Re-arranging the above equation we get,

𝑛2 ℎ2 𝜀0
𝑟=
𝑍𝑒 2 𝑚𝜋
𝑛2 ℎ2 𝜀0
On solving (and putting Z=1 for hydrogen atom) we get: 𝑟= 2 For radius of innermost orbit, put n=1
𝑒 𝑚𝜋
ℎ2 𝜀0
𝑟= 2 = 𝑎0 Where 𝑎0 is the radius of Hydrogen Atom
𝑒 𝑚𝜋
 Energy of Orbits:
The orbital energy of orbiting electron in the discrete energy levels in the Bohr’s model is called as the energy
of orbits. We already know, from Rutherford’s Model that total energy(T) is given by

1 𝑍𝑒 2
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = −
8𝜋𝜀0 𝑟
𝑛 2 ℎ 2 𝜀0
Putting the value of Bohr’s radius 𝑟 = , we get
𝑒 2 𝑚𝜋
1 𝑍𝑒 4 𝑚𝜋 1 𝑍𝑒 4 𝑚
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = − 2 2
=−
8𝜋𝜀0 𝑛 ℎ 𝜀0 8 𝑛2 ℎ2 𝜀0 2
𝑍𝑒 4 𝑚
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = −
8 𝑛2 ℎ2 𝜀0 2
Putting the values of electron mass(m), charge(e), permittivity of free space(Ɛo), Planck’s constant(h); we get.
13.6
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = − 2
𝑛
We know the third postulate of Bohr’s model.
An electron might make a transition from one of its specified non-radiating orbits to another of lower
energy. When it does so, a photon is emitted having energy equal to the energy difference between the initial
and final states. The frequency of the emitted photon is then given by .

ℎν = 𝐸𝑖 − 𝐸𝑓

We have an energy equation,

𝑍𝑒 4 𝑚
𝐸=−
8 𝑛2 ℎ2 𝜀0 2
𝑍𝑒 4 𝑚 𝑍𝑒 4 𝑚
ℎν = −
8𝑛𝑖 2 ℎ2 𝜀0 2 8𝑛𝑓 2 ℎ2 𝜀0 2

Re arranging the equation, we get

𝑍𝑒 4 𝑚 1 1
ℎν = −
8 ℎ2 𝜀0 2 𝑛𝑖 2 𝑛𝑓 2
 𝑍𝑒 4 𝑚 1 1
ℎν = 2 2 2 − 2
8 ℎ 𝜀0 𝑛𝑖 𝑛𝑓

Re arranging the above equation we get

𝐶 𝑍𝑒 4 𝑚 1 1
= 3 2 2
− 2
λ 8 ℎ 𝜀0 𝑛𝑖 𝑛𝑓

1 𝑍𝑒 4 𝑚 1 1
= −
λ 8 𝐶 ℎ3 𝜀0 2 𝑛𝑖 2 𝑛𝑓 2

𝑍𝑒 4 𝑚
Where =R
8 𝐶 ℎ 3 𝜀0 2
1 1 1
=𝑅 2− 2
λ 𝑛𝑖 𝑛𝑓

Which is similar to Balmer relation.

 DRAWBACKS OF BOHR’S MODEL:
• It was primarily for hydrogen atom
• It couldn’t elaborate spectra of multi-electron atoms
• Wave nature of electron was not justified by the model (inconsistent with the de Broglie’s hypothesis of
dual nature of matter)
• It didn’t illustrated molecules making process of chemical reactions
• It violated Heisenberg’s Principal(Δx × Δp ≥nh/(2π)) which said that it was impossible to evaluate the
precise position and momentum of electron (and other microscopic particles) simultaneously. Only
their probability could be estimated.
• Zeeman effect(spectral lines variation due to external magnetic field) and Stark Effect(spectral lines
variation due to external electric field) couldn’t be described by the model