X - Ray Diffraction Method
When a beam of X – rays are fall on a crystal atom or ions producing diffraction.
The diffracted beam of X-rays are photographed and analyzed to get idea about the
internal structure of crystalline solids.
Bragg’s Law:
W.H. Bragg and his son W.L. Bragg showed that When X-rays are made to fall on
a crystal; they get reflected by the atomic planes present inside the crystal. Now X – rays
are said to be diffracted by the crystal. The diffracted beam of X-rays will behave as if it
had been reflected from the surcace of the crystal. The intensity of the diffracted beam at
certain angles will be maximum when two different planes reinforce each other. This is
possible when the path difference of the two waves is an integral multiple of wavelength
of X – Rays.
Bragg developed a simple relation between the wavelengths of X – rays and the
interplanar distance in a crystal.
2 d sin ϴ = n λ
Where,
λ – Wavelength of X – rays
n – Order of reflection (n = 1, 2, 3, …)
ϴ - Angle of incidence or Angle of scattering
Knowledge of λ and ϴ where maximum intensity of the diffraction waves occurs
would enable one evaluate d.
There are two principal methods used for analyzing crystal structure by X – ray
diffraction. They are:
1. Rotating Crystal Method
2. Powder Method
1
Rotating Crystal Method
Principle:
When a beam of X – rays is allowed to strike the face of a crystal, it gets
diffracted. The diffracted beam is capable of making impression on a photographic film
in the form of a spot. If the crystal is rotated, various planes come successively into
position for diffraction to occur and spots of different intensities and size appear on the
film. The bright spots are obtained from those planes which contain a large number of
atoms and for those values of ϴ which satisfy the Braggs relation.
Working:
A narrow beam of X – rays is made to strike the face of a crystal which is mounted
on a graduated turn table through a glancing angle ϴ. The diffracted rays are
photographed.
Then the value of glancing angle is increased by rotating the table about an axis
parallel to one of the crystal axes, (say X - axis). The diffracted rays at different glancing
angles will produce spots of different intensities and size.
Similar photographs are taken by rotating the crystal about an axis parallel to each
of the other axes of the crystal (Y – axis and Z - axis). From the intensities, sizes and
positions of the various spots obtained, the crystal structure is worked out.
2
Powder Method
Principle:
The rotating crystal method of analyzing the crystal structure the process of
mounting the crystal on a precise axis is laborious and time consuming. This difficulty is
overcome by making use of a fine crystalline powder instead of a single crystal.
The crystal powder contains a large number of minute crystals oriented randomly. That
is, the crystal planes are oriented at all possible angles to a beam of X – rays. However,
there will always be some crystals having their planes properly oriented at the correct
angle to give reinforced waves.
Working:
A narrow beam of X – rays is made to strike a sample of crystal powder taken in a
thin walled glass capillary tube. A cone of diffracted radiation is produced. This appears
on a strip of photographic film around the capillary in the form of a circular arcs on either
side of the bright spots at the centre (the centre spot is due to undiffracted radiations).
3
The distance between each pair of arcs corresponds to the order of diffraction for a
set of planes. If ϴ is the glancing angle, 2 ϴ will be the diffraction angle which is
calculated from the positions of the film and the arcs on it using the formula
x
2 ϴ=
r
Where,
x - Distance between an arc from the centre spot
r - Distance between the capillary tube and the photographic film.
From the known values of n and ϴ, the interplanar distance d is calculated
and the crystal structure is worked out.
