Rutherford atomic model

In this experiment, very high energy α- particles from a radioactive source were scattered
on a very thin gold foil having a thickness of 0.00004 cm.The scattered α- particles
produced tiny flashes on striking with circular Zinc sulphide (ZnS) screen placed behind
the gold foil. These striking give scintillation (flash) on the ZnS screen.These was observed
by movable microscope. The apparatus was evacuated ( vacuum creation) to avoid the
scattering α- particles due to air .

Draw figure from book

Observation

It was found that,

i) Most of α- particles (99%) travelled in a straight line.

ii)Few α- particles were deflected by small angles.

iii)Very few α- particles were deflected by larger angles or even retracted their original
path.

Postulates

On the basis of observations, Rutherford gave following postulates to explain the structure of atom.

• Most part of an atom is empty

• The entire mass of atom is located on the central part

• Positive charge is located on the central part of the atom.

• Volume occupied by the nucleus is very small as compared to the total volume of an atom

• The total number of positive and negative charge in an atom is equal i.e. an atom is
electrically neutral.

Conclusion
 • Rutherford considered an atom as a miniature solar system in which electrons always
revolve around the positively charged nucleus in different circular paths like planets
revolve around the sun. Hence, this model of atom is also called planetary atomic model.

Limitation

1. It could not explain the stability of atoms.

It does not obey the Maxwell theory of electrodynamics. According to it, "A small charged
particles moving around an oppositely charged center continuously loses its energy in the form of
radiation." Therefore, the revolving electron should continuously lose its energy. As a result of
this, its revolving path should become smaller and smaller. Thus, the path of the revolving electron
should be spiral as shown in figure and ultimately collapse into the nucleus. Hence, atom must be
unstable but atoms are quite stable. (draw figure from book)

2. It could not explain the origin of discontinuous atomic spectra.

If revolving electrons loses energy continuously in the form of radiation, the spectrum must
be continuous but the atomic spectrum is discontinuous or discrete.

Planck quantum theory

Planck quantum theory is also called black body radiation.

Postulates

• The emission of radiation by a black body is due to the vibration of charged particles.

• The energy emission is not continuous but in discrete packets of energy called quanta

• The emitted radiation propagates in the form of waves.

• The energy associated with each quantum number for a particular radiation of frequency is
given by E = h𝞾

Where h = planck's constant = 6.62 ˟ 10-34 Js, 𝞾 = frequency of radiation

 Bhor's atomic model

Postulates

• In an atom, electrons revolve around the nucleus in a certain definite circular path called
orbits or shells.

• Each orbit is associated with definite amount of energy and electron holding capacity (2n2).
There are different shells around the nucleus and have different energies. Energy of the
orbit increases with the increase in distance from nucleus.

• As long as the revolving electron remains in the same shell the energy of electron does not
change. Therefore, these orbits are known as stationary states or energy level. It justifies
the stability of atom.

• Those orbits are permitted for which the angular momentum of a revolving electron is equal
to the positive integral multiple of h/2𝞹 i.e. mvr = nh/2𝞹 ( m = mass of electron, h= planck
constant , n= number of shells) It explains the quantization of angular momentum of the
revolving electron.

• Absorption and emission of energy in the form of radiation takes place when the revolving
electron jumps from one energy level to another energy levels.( Draw figure from book)

• Electrons gets promoted to a higher energy level by absorbing a proper quantum of energy
and the electrons loses the energy when its jumps to one of the lower energy levels. In such
case , 𝞓E = E2- E1= hv = h c/𝞴 Where h = planck's constant , v = frequency of radiation ,
E2= higher energy level, E1= lower energy level, C= velocity of light , 𝞴= wavelength

• It explains the origin of atomic spectrum.

Origin of Hydrogen spectrum

When an electric discharge is passed through a discharged tube containing H2 gas at low pressure,
then molecular H2 first splits into atomic hydrogen, which further gains energy. Then the electron
from the atom jumps from lower energy level (called ground state) to higher energy level (called
excited state). Depending upon the amount of energy absorbed by the electrons, the electrons can
jump from 1st, 2nd, 3rd excited state and so on… Excited electron cannot stay in higher energy level
for longer period of time and it returns to the lower energy level. (Draw figure from book). During
this process, it emits energy in the form of radiation having different wavelengths. The wavelength
of the emitted radiation depends on the energy difference between higher and lower levels. When
emitted electrons are passed through the prism, it gives a spectrum of different radiations called
the hydrogen spectrum. (Draw figure from book)

The wavelength of all the lines in the series can be calculated by using Ritz equation, i.e

1 1 1
𝜐̅ = = 𝑅 [ − ]
𝜆 𝑛1 2 𝑛2 2

Where 𝜐̅ = wavenumber (cm-1 ) , R = Rydberg constant= 109677cm-1 , n1 = lower energy level , n2

= higher energy level , 𝞴 = wavelength of emitted radiation

Limitations

1. It could not explain about the fine structure or existence of additional quantum numbers.

2. It could not explain about the spectra of multi-electron system like He, He+, Li, Li+, etc.

3. It was unable to explain the movement of electron in three-dimensional space.

4. It could not explain about Zeeman and Stark effect.

(The splitting of spectral line into finer lines due to the presence of magnetic field is called
Zeeman effect.)

(The splitting of spectral line into finer lines due to the presence of electric field is called
stark effect.

5. It failed to explain about the ability of atoms to form molecules by chemical bonds.

• Explain about the different types of series formed in hydrogen spectrum? ( copy from book)

Elementary idea of quantum mechanical model

Bhor gave an idea about the stationary energy level around the nucleus. De-Broglie
equation concluded that small particles like electrons, photons, and atoms can act as both
waves and matter. Heisenberg's uncertainty principle gave an idea for describing the
 position and momentum of electrons. Schrodinger combined all these ideas and a
developed a new model of atoms known as the quantum mechanical model. The solution
of Schrodinger wave equation (quantum mechanical model) was able to explain the actual
position of electrons around the nucleus with the help of quantum number.

De-Broglie equation

De-Broglie equation has been derived by combing Einstine's mass-energy relation and planck's
photon-energy relation. It explains about the wave-particle duality.

According the Einstine,

E = mc2………………(i)

Where m = mass of particle, c= velocity of light

According the planck,

E = h𝞾………………(ii)

Where h = planck's constant, 𝞾 = frequency of radiation

Equating (i) and (ii) we get,

mc2 = h𝞾
𝑐 𝑐
mc2 = h𝜆 (𝞾 = 𝜆)

ℎ
mc = 𝜆

ℎ
i.e. 𝜆 =
𝑚𝑐

ℎ
𝜆 =𝑝 ( p = mc = momentum of particle)

ℎ
i.e. 𝜆 = 𝑝

1
𝜆 α𝑝
This is the required De- Brogeli's equation.

From this relation, it is concluded that if wave character of any matter increases then its
particle character decreases and vice-versa.

Significance

The wave character of large objects in motion has no practical significance because their
wavelength is too small to measure. From this relation, it is concluded that if wave
character of any matter increases then its particle character decreases and vice-versa.

Heisenberg's Uncertainty principle

It states that, " it is impossible to calculate the position and the velocity or the momentum
of small particle accurately at the same time".

If an attempt is made to determine the position of a moving electron by throwing light of

shorter wavelength on it, the electron changes its velocity for light wave strike the electron.

If light of longer wavelength is thrown, the position of electron is changed as light of longer
wavelength takes more time to return to the eyes of the observer.

Mathematically, if 𝞓x and 𝞓p are the position and momentum respectively, then,

ℎ
𝞓x . 𝞓p ≥ 4𝜋 ………………(i)

It can be seen that if the uncertainty in momentum increases then the uncertainty in position
decreases and vice-versa.

Since momentum = mass 𝞦 velocity

𝞓p = m . 𝞓v ……………..(ii)

Equation (i) can be written as

ℎ
𝞓x . m . 𝞓v ≥ 4𝜋

ℎ
Or, 𝞓x . 𝞓v ≥ 4𝜋𝑚 ……………………….(iii)
Equation (iii) clearly shows that uncertainty is more pronounced in the case of particles
having small masses, viz, electrons, protons, neutrons, etc.

Concept of probability

According to the Heisenberg's uncertainty principle, it is impossible to find the exact

position and momentum of electron in an atom at an instance. This implies that an electron
cannot travel around the nucleus at a constant velocity in a fixed orbit of definite radius.

Therefore, an electron has a greater possibility of finding itself around the nucleus in a
wider space, which is known as the probability concept of an electron in an atom. This
shows that idea of bhor's definite orbits does not appear to hold good in the light of
uncertainty principle.

Hence uncertainty principle suggests that an electron moves in the whole space around the
nucleus, but remain most of the time within a small volume around the nucleus, where the
probability of locating the electron is maximum. This probability gave an idea of atomic
orbitals, which provide a wider space around the nucleus for the movement of electrons.
 Concept and shapes of s, p, d, f orbitals

Orbitals is a three-dimensional space around the nucleus where probability of finding

electrons is maximum. An orbital can hold a maximum of two electrons with opposite
spins.

A shell is a direction that electrons take through the nucleus of an atom.

A subshell is the field of a shell where electrons pass.

(Draw figure from book for s and p orbitals)

s- orbitals

• s-orbitals has spherical shape

• Each shell has one s orbital.

• s-orbital is spherically symmetrical

It means the possibility of finding an electron around the nucleus in a certain region in all
possible directions.

p- orbitals

• 1st shell has no p subshell.

 • P-subshell has three orbitals, i.e. px , py and pz .

• Each p orbital has dumbbell shape.

• The px orbital is symmetrical around x-axis. This, means there is possibility of finding
electrons only in certain space along x-axis.

• Each orbital can hold maximum of two electrons.

d- orbitals

• d orbital start from 3rd shell

• d subshell consists of five orbitals i.e. dxy , dyz , dzx , 𝑑𝑥2-y2 , 𝑑z2

• d orbital has double dumbbell shape.

• Each orbital can hold maximum of two electrons

f- orbitals

• f orbital start from 4th shell

• F subshell consists of seven orbitals

• f orbital has complex structure.

• Each orbital can hold maximum of two electrons.

Quantum numbers

The parameters which are used to describe each electron in an atom are called quantum numbers.

The quantum numbers give the identification (address) of an electron in an atom by specifying its
main shell (n), subshell (l) , space orientation (m) and direction of spin (s).

There are four sets of quantum numbers as,

a) Principal quantum number (n)

b) Azimuthal quantum number (l)

 c) Magnetic quantum number (m)

d) Spin quantum number (s)

Principal quantum number (n)

• It represents the main energy level or shell of an atom to which the electron belongs.

• It can have only positive whole number values.

• It characterizes the energy of electron and size of the shell where electron resides.

b) Azimuthal quantum number (l)

• It describes about the sub-shell where the electron belongs.

• Its value ranges from 0 to (n-1), i.e., l = 0 to (n-1).

• The different sub-shell are s, p, d, and f having energies increasing in the order of s < p <
d < f.

• The total number of possible sub-shell in each shell is numerically equal to the value of 'n'

• It characterizes the shape of the subshell where electron resides and relative energy of the
electron.

• The quantum numbers are also known as azimuthal quantum numbers since the angular
momentum of the electron depends upon the value of azimuthal quantum number.

• Angular momentum of orbital in the given orbital = l ( l+1)1/2 ħ where ħ = h/2𝞹

For n =1 (k shell) For n = 2 ( L shell)

l = 0 to ( 1-1 ) l = 0 to ( 2-1 )

=0 = 0 ( 2s ) , 1 (2p ) (two subshell)

∴ l = 1 s ( 1 sub – shell )

For n = 3 (M shell) For n = 4 (M shell)

l = 0 to ( 3 -1 ) l = 0 to ( 4 -1 )

= 0 ,1 , 2 = 0, 1, 2, 3

= 3s, 3p, 3d (three sub-shell) = 4s, 4p, 4d , 4f ( four sub-shell)

a) Magnetic quantum number (m)

It gives information about the number of orbital where the electron belongs in the given subshell
and their orientation in the space .

Maximum number of orientation is given by (2l +1 ) and its value ranges from –l to + l through
zero.

It characterizes the orientation of the orbitals where the electrons resides.

 d) Spin quantum number (s)

Electron revolves around the nucleus .

So, it has its own spin.

Among the pair of electron in each orbital one electron has clockwise spin (i.e. ↿ or + ½ ) and the
other has anti clockwise spin (i.e. ⇂or – ½)

It characterizes the spin of the electron.

Aufbau principle

According to this principle, electrons are arranged in different subshells in order of increasing
energies of such subshells. , i.e. electrons are first filled in lower energy containing orbitals and
gradually into higher energy containing orbitals.

Energy level of orbitals can be estimated through the following arrangement of the orbitals.The
increasing order of energies of different subshell is = 1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s and so
on.

a) 4s comes before 3d can be explained by (n +l ) rule.

According to this rule, the orbitals having lesser value of (n +l ) has to be filled first.

Illustration

For 4s ; (n +l ) = (4 +0 ) = 4

For 3d ; (n +l ) = (3 +2 ) = 5
Since 4s, subshell has lower value of ( n + l ) than 3d subshell, therefore 4s is filled up first.

b) When two electrons have same (n +l ) value, the orbitals with lower value of n has
lower energy.

Let us compare the (n +l ) value for 3d and 4p orbitals.

For 3d ; (n +l ) = (3 +2 ) = 5

For 4p ; (n +l ) = (4 +1 ) = 5

Here, both 3d and 4p orbitals have same (n +l ) value but 3d orbitals has lesser value of n and
hence it has lower energy than 4p orbitals.

Therefore , 3d orbitals has to be filled before 4p orbitals = (4 +0 ) = 4

Exceptions

In case of chromium and copper, the actual electronic configuration is slightly different than the
configuration according to Aufbau principle.

a) Chromium (Cr)

24Cr = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d4 (Expected)

But, 24Cr = 1s2, 2s2, 2p6, 3s2, 3p6, 3d5, 4s1 (Actual)

b) Copper

29Cr = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d9 (Expected)

29Cr = 1s2, 2s2, 2p6, 3s2, 3p6, 3d10 , 4s1 (Actual)

This is due to the fact that, " half-filled and completely filled subshell are more stable than
incompletely / partially filled subshells."
 Pauli's exclusion principle

It states that, " no two electrons in an atom can have same set of all the four quantum numbers.

If two electrons have same value for n , l, and m value of spin than the value of spin quantum
number (s) must be different i.e. + ½ for one electron and – ½ for another electron.

Example ( copy from book)

Hund 's rule of maximum multiplicity

It states that, " paring of an electron in any degenerate orbitals takes palce only after the orbitals
are filled by single electron with same spin.

Example (copy from book)

Degenerate orbitals

The orbitals having equal energy with different orientations are called degenerate orbitals. For
example, p orbitals has 3 degenerate orbitals named px , py ,pz .Similarly d and f orbitals have 5
and 7 degeneracies respectively.

Bhor Bury principle.

The maximum number of electrons that can be accommodated is calculated by Bhor Bury
principle.

According to this principle,

• The maximum number of electrons that can be accommodated in a shell is principle

quantum number or number of shells.

• The valance shell cannot accommodate more than 8 electrons

• A new orbit begins to fill when the outermost orbit gets 8 electrons

• The penultimate shell cannot accommodate more than 18 electrons