Atomic structure

Rutherford’s atomic model

After the discovery of different subatomic particles, the designation of these

subatomic particles as constitutes of an atom became the part of query. Different
types of atomic models were proposed. J.J Thomson proposed Plum Pudding (or,
Watermelon model) in 1898 but this atomic model could not justify many issues
like origin of spectra and others. In 1911, Rutherford proposed an atomic model
based on α-particle scattering experiment. This is called Rutherford's α-scattering
experiment or simply Rutherford's atomic model.
Experimental arrangement
α-particles were produced from a radioactive source such as polonium
kept in a lead cavity. These α-particles were bombarded on a thin gold foil
. The fate of the α-particles scattered from gold foil to the screen coated
with zinc sulphide were studied by using a movable screen. When α-
particles were striked on the thin gold foil, a flash of light, called
scintillation, was produced on the screen due to fluorescence which could
be seen with the movable microscope. The whole apparatus was arranged
inside a vacuum chamber to prevent the scattering of α-particles by air.

Figure: Rutherford alpha scattering experiment

observation:
a. Most of the α-particles (about 99%) passed through thin gold foil
without any appreciable deflection.

b. Some α-particles were found to undergo appreciable deflection.

c. A very small number of α-particles (about 1 in 10,000 to 1,00,000)

were deflected through angles more than 90° or suffered deflection of
nearly 180°.
Inferences:

after Observing the scattering of α-particles, scattering, Rutherford made the following
conclusions.

a. Since most of the α-particles passed through the gold foil undeflected it means that there
must be a very large empty space with in the atom. In other words atom is mostly empty.

b. α-particles are positively charged and have considerable mass. They can be deflected only if
they come close to some heavy positively charged mass due to force of repulsion.

c. The strong deflection or even bouncing back of alpha particles from the gold foil must be the
closer encounter of alpha particles with the massive positively charged present in the atom.

d. Since protons are concentrated in a very small space (nucleus), electrons must revolve
round the nucleus so as to counter balance the centripetal force by centrifugal force of
revolving electrons.
Rutherford nuclear model of atom:
On the basis of above experiment and observations, Rutherford proposed a
model for the structure of of the atom called Rutherford nuclear model of
atom. the main points are :
1. The entire mass and the positive charge is concentrated in a very small
region at the centre in an atom called nucleus.
2. The magnitude of the positive charge on the nucleus is different for
different atoms.
3. The nucleus is surrounded by negatively charged electrons which balance
the positively charge on the nucleus.
4. Most of the space in an atom between the nucleus and the revolving
electrons is empty.
Limitations of Rutherford’s atomic model

Though the Rutherford's atomic model gave the clear concept of nucleus in atom, it
suffers from the following limitations.

a. Rutherford’s atomic model couldn’t explain the stability of atom

b. Rutherford’s atomic model couldn’t explain the origin of line spectra of atoms

c. This model is against the currently accepted wave mechanical model of an atom.
Explanation of hydrogen spectra based on the Bohr’s atomic model
Spectra
The arrangement of wavelength or frequency of radiations in increasing or
decreasing order is spectrum (plural = spectra).

Though hydrogen spectra was observed as early as in 1880, neither atomic model
could explain satisfactorily before 1913. Bohr's atomic model is able to explain the
major aspects of hydrogen spectra at that time. According to Bohr's atomic model,
electron jumps to higher energy level (n2) by the absorption of certain amount of
energy from its ground energy level (n1). When the electron returns from n2 shell
having energy E2 to n1 shell having energy E1, the energy released is given by, ΔE =
E2 – E1
hυ = E2 – E1 [... ΔE = hυ]

These radiations when observed through spectroscope, bright lines of

colours are obtained. These lines are called the spectral lines of a
spectrum. In hydrogen spectrum, discontinuous lines of colours are
observed exhibiting definite waves of selected wave lengths. Wave
lengths and wave numbers of the radiations of Balmer series (in visible
region). Based on the relation, different types of spectral lines observed
in hydrogen spectra are diagrammatically shown in the following figure.
Fig: spectral series of hydrogen spectrum
Each types of hydrogen spectra is briefly discussed below.

a. Lyman series: When electrons jump from any higher energy level (n2 =
2,3,4,5,...,∞) to the first energy level (n1=1), the released energy comes in the form
of radiations in UV-region (92 to 120 nm). This series of spectral lines is called
Lyman series.

b. Balmer series: When electrons jump from any higher energy level
(n2=3,4,5,...,∞) to the second energy level (n1=2), the released energy comes in the
form of radiations in visible region (400 to 650 nm). This series of spectral lines is
called Balmer series
c. Paschen series: When electrons jump from any higher energy level
(n2=4,5,6,...,∞) to the third energy level (n1=3), the released energy
comes in the form of radiations in infrared region (950 to 1875 nm).
This series of spectral lines is called Paschen series.

d. Brackett series: When electrons jump from any higher energy level
(n2=5,6,7,...,∞) to the fourth energy level (n1=4), the released energy
comes in the form of radiations in far infrared region (1945 to 4050
nm). This series of spectral lines is called Brackett series.
e. Pfund series: When electrons jump from any higher energy level
(n2=6,7,8,...,∞) to the fifth energy level (n1=5), the released energy
comes in the form of radiations in far infrared region (above 4050 nm).
This series of spectral lines is called Pfund series.
Limitations of Bohrs theory:
Bohrs atomic model had successfully explained the origin of hydrogen
spectrum and was to remove the defects of Rutherford atomic model.
However it has following drawbacks
1. This theory cannot explain the line spectra of other polyelectron atoms.
2. According to bohr the circular orbits of the electrons are planer. However
this is not true and the electron move around the nucleus in three
dimensional space.
3. It cannot explain the zeeman effect and stark effect.
4. It fails to explain the cause of chemical combination and shape of
molecules.
Zeeman and stark effect:
The splitting of spectral line in presence of magnetic field is called
Zeeman effect and the splitting of spectral line in presence of electric
field is called Stark effect.
Schrödinger wave mechanics: Schrodinger wave equation
To describe the mechanics of particle wave, Schrödinger developed a
mathematical equation in 1926. This equation is based on the
probability concept and idea of electron as stationary wave
(standing wave) around the nucleus.
Applications of Schrödinger wave equation (mechanics)

The Schrödinger wave mechanics has various applications. Some of the applications
are given
below.
a. It introduces the concept of atomic orbitals.

b. It develops three quantum numbers. These are principal quantum number (n),
azimuthal
quantum number (l), and magnetic quantum number (m).

c. It explains the Zeeman effect and Stark effect.

d. It is useful to derive the energy expression for hydrogen and helium atoms.
de-Broglie wave equation

In 1905, Albert Einstein suggested the dual nature of light. According to this
concept, light possesses the wave nature and particle nature (E = mc2). In
1924, de-Broglie advanced the idea that not only photons or light but also
any matter (like electron) shows dual nature of wave and particle. The wave
associated with matter is termed as matter wave or de- Broglie wave.
Electron shows the particle nature as well as wave nature. Beams of
electrons passed in electron microscope shows wave nature. The wave-
particle duality of matter led de-Broglie to derive the relation λ = h/p which
includes the wave nature and particle nature of matter in motion.
Derivation of de-broglie wave equation:

Where m = mass of electron

c =velocity of light
f= frequency
/l = wavelength of radiation
h= Planck’s constant
Significances of de-Broglie equation

The significance of the de-Broglie equations are as

follows.

1. The de-Broglie equation shows the relation between

particle character and wave character of matter.
2. The de-Broglie wave equation is applicable for all
matter however it is more significant for microscopic
particle. In case of macroscopic particle, the value of
wavelength is less significant.

3. It helps to deduce the Bohr’s condition for quantization

of angular momentum of electron.
Differences between particle and Wave
nature

Particle Wave
1. A wave spreads
in space.
(wave is
1. A particle occupies a particular space.
delocalized in
(Particle is localized in space)
space)
e.g. A pen occupies a particular space.
e.g. Sound of mike
reaches
everywhere.
2. Two or more
2. No two or more particles occupy the waves can co-
same space exist at the same
at the same time. i.e. particles do not region at the
exhibit same time. Waves
interference. exhibit
interference.
Heisenberg uncertainty principle

Heisenberg uncertainty principle states that, it is impossible to

determine the position and momentum or velocity of microscopic
particle in motion simultaneously and accurately.
Alternatively, two conjugate properties of a microscopic particle in
motion cannot be determined exactly and simultaneously. Such
conjugate properties may be position and momentum, time and
energy, etc
Mathematically, Heisenberg uncertainty principle can be expressed as
Δx.Δp ≥ h/2π
Where, Δx = uncertainty or error in the measurement of position

Δp = uncertainty or error in the measurement of momentum

h = Planck’s constant (h = 6.626 × 10-34 Js)

If position of electron is measured with absolute accuracy, Δx=0
Δp ≥ h/2π . Δx
Δp ≥ h/2π . 0
Δp ≥ infinity
This means error in determination of momentum is infinite.
Similarly , when Δp=0 ; Δx ≥ infinity
This means error in determination of position is infinite.
Applications of uncertainty principle

a. It is the fundamental principle of quantum mechanics.

b. The equation is useful to determine the limit of accuracy regarding precise measurement of
position and momentum of microscopic particles.
c. This law enables to show that electron does not exist in the nucleus.

Limitation of uncertainty principle

The Heisenberg uncertainty principle is applicable for microscopic particles but not for
macroscopic particles because the error in the measurement of position and momentum are
negligible for macroscopic particle. The momentum transforming effect of photon of light is
significant for microscopic particle but not for macroscopic particles.