Atomic Spectrum:
The splitting of light into series of colour band is called dispersion and the series of colour
band is called spectrum.
Continuous Spectra: Spectrum that have continuity of colurs i.e. colours are so continuous that
merges into the next without any gap . Hence, the spectrum is called continuous spectrum.
Emission Spectra: The spectrum of radiations emitted by a substance that has absorbed energy.
Line Spectra: The emission Spectra that emits light at specific wavelength with dark spaces
between them.
Absorption Spectra: A radiation of light that passed through a sample that absorbs radiations of
certain wavelength , the missing wavelength absorbed by the matter leave dark spaces in
continuous spectra.
Line Spectrum of Hydrogen Atom
Electric discharge when passed through hydrogen it produce energetically excited hydrogen atom
that emits EMR of discrete frequencies that consists of series of lines known as hydrogen spectrum.
Johannes Rydberg observed all series of lines in the hydrogen spectrum and described by the
following expression:
R = Rydberg constant R = 109678 cm–1
Bohr’s Model:
(i) The electrons revolve around the nucleus in a definite circular paths called orbits.
(ii) Each orbit is associated with definite energy known as energy levels or energy shells
numbered as 1, 2, 3, 4……….. or K, L, M, N……….
(iii) Electron revolve in those orbit for which angular momentum is a whole number
multiple of h/2π.thus, (mvr) = nh/2π (n = 1, 2, 3, 4 etc).
(iv) As long as electron is present in a particular orbit, it neither absorbs nor loses energy
and its energy, therefore, remains constant.
(v) When energy is supplied to an electron, it absorbs energy and jumps to higher energy
state and when it comes to lower energy state it emits energy .Thus frequency change
∆𝐸
between two stationary states that differs in energy is given by: 𝜈 = ℎ
2
(vi) The radii of an stationary states are measured as: rn = n a° where a° = 52.9 pm as n
increases the value of r increases. For hydrogen like species rn = 52.9(n2)/Z
(vii) The energy of its stationary states is given by the expression: En = -RH (1/n2) where
RH = 2.18 ×10-18 J . For hydrogen like species En = -RH (Z2/n2) J
** When the electron is attracted by the nucleus and present in n orbit, the energy is emitted
and its energy decreases results in the presence of negative sign.
(viii) Velocity of electron increases with increase of positive charge on the nucleus and
decreases with increase in the value of n.
Limitations of Bohr’s Model
(i) The theory could not explain the atomic spectra of atoms containing more than one
electron or multielectron atoms.
(ii) Bohr’s theory failed to explain the fine structure of the spectral lines.
(iii) Bohr’s theory could not explain the splitting of spectral lines in magnetic field( Zeeman
effect) and Splitting of lines in electrical field(Stark effect).
(iv) Bohr’s theory failed to explain the ability of atoms to form molecule formed by chemical
bonds.
(v) It was not in accordance with the Heisenberg’s uncertainty principle.
Dual Behaviour of Matter (de Broglie Equation)
de Broglie in 1924, proposed that matter, like radiation, should also exhibit dual behaviour i.e.,
both particle like and wave like properties. This means that like photons, electrons also have
momentum as well as wavelength.
Assume light have wave nature, then its energy should be given by Planck's theory
E=hν …(i)
If it have particle nature, then its energy should be given by Einstein relation
E = mc2 …(ii)
On comparing equation (i) and (ii),
E = mc2 …(ii)
On comparing equation (i) and (ii),
hν=mc2
λ=h/mc (for light) …(iii)
For other matter,
λ=h/mv …(iv)
λ=h/p …(v)
where p = momentum
This equation is called de- Broglie equation.
Significance of de-Broglie Equation:
It is significant for macroscopic bodies only as the wavelength associated with ordinary object
are so short due to their large masses as their wave properties cannot be detected thus have no
wavelength.
Heisenberg’s Uncertainty Principle
It states that, “It is impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron”.
Significance of Uncertainty Principle
(i) It depicts the existence of definite paths or trajectories of electrons.
(ii) The effect of Heisenberg’s uncertainty principle is significant only for microscopic objects
and is negligible for macroscopic objects.
Quantum Numbers
There are a set of four quantum numbers which specify the energy, size, shape and orientation of
an orbital.
(i). Principal quantum number (n)
It identifies shell, determines sizes and energy of orbitals. It is indicated by ‘n’ and its values are
1, 2, 3, 4...
Azimuthal or Subsidiary or Orbital Angular Quantum Number (l) :
It identifies sub-shell, determines the shape of orbitals, energy of orbitals in multi-electron atoms
along with principal quantum number and orbital angular momentum, i.e., The number of orbitals
in a sub shell = (2l + 1). Its value ranges from 0 to (n-1).
(iii). Magnetic quantum number (m):
the magnetic orbital quantum number determines the number of orbitals present in any subshell.
Its values ranges from – l ,0, + l
Thus, for energy value of l, m has 2l + 1 values. For example,For l = 0 then m = 0.i.e. s-subshell
has only one orientation or has only one orbital called s-orbital.
Electron spin quantum number (ms)
It refers to orientation of the spin of the electron. It can have two values +1/2 and -1/2. +1/2
identifies the clockwise spin and -1/2 identifies the anti-clockwise spin.