CHEM F313: Instrumental Methods of Analysis

Lecture 23
X-ray Diffraction Analysis
Outline
 Last Class

 What is X-ray Powder Diffraction?

 How to produce X-ray diffraction
 Characteristic X-rays

 Today’s Class

 Monochromatic X-Ray
 Scattering of X-ray by an atom
 BRAGG’s law
 Lattice planes, Miller indices
 Primitive and Non-Primitive Lattice
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Characteristics X-rays energies
Moseley's law
In brief, the law states that the square root of the frequency of the
emitted x-ray is approximately proportional to the atomic number.

Target Metal  of K radiation (Å)

Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
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Monochromatic X-Ray
• Electron beam provided by the heated W filament, is accelerated
towards an anode by a potential difference of 30 kV.
• The electron strikes the target and a spectrum of X-rays is emitted
• The Chamber is evacuated to avoid collision between air particles
• The X-rays leave the tube through the Be window. The absorption of
X-rays on passing through materials depend on the atomic weight of
the elements present in the material. Be having atomic number 4 is
the most suitable window material.

Name an effective material

to shield the X-rays

Pb

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Monochromatic X-Ray
While Operation is going on, Cooling of the anode is necessary----WHY??
Only small fraction of the energy of the incident electron beam is
converted to X-rays. Most of the energy is converted into heat and the
anode would soon melt of it is not cooled properly.
FILTRATION: We need monochromatic X-ray not the continuous
spectrum
 In the spectrum of X-rays emitted by copper, the Kα is the most
intense and need to filter out all the other wavelengths, leaving the
Kα line for diffraction experiments.
 For copper radiation a sheet of Ni foil is very effective for such
separation.
 The energy require to ionise 1s electrons of Ni = 1.488 Å, which lies
between the values for the Kα and Kβ line of the copper emission
spectrum. 5
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Monochromatic X-Ray
 Cu Kβ radiation therefore has sufficient energy to ionise 1s electrons
of Ni whereas Cu Kα does not.

 The Ni foil is effective in absorbing the Cu Kβ radiation and most of

the white radiation.

 It results in a monochromatic clean beam of Kα radiation.

 A lighter element such as Fe would absorb both Kα radiation as well

as Kβ. Because its absorption edge is displaced to higher
wavelengths.

 On the other hand a heavier element such as Zn would transmit

both Kα and Kβ radiations of while still absorbing much of the higher
energy white radiation. 6
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Scattering of X-rays

 X-rays beam directed, interacts with the electrons of the crystal atoms
 Electrons oscillate under the influence of the incoming X-Rays
 Become secondary sources of EM radiation, in all directions
The waves emitted by the electrons have the same frequency 
coherent
 The emission undergo constructive or destructive interference

Secondary
Incoming X-rays emission

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Scattering of X-ray by an atom

Electron cloud oscillates Nucleus also oscillates

weak effect  neglected
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Scattering of X-ray by atomic planes
Crystalline materials are characterized by the orderly periodic
arrangements of atoms.

The (200) planes The (220) planes

of atoms in NaCl of atoms in NaCl

•The unit cell is the basic repeating unit that defines a crystal.
•Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
–These crystallographic planes are identified by Miller indices.
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Scattering of X-ray by atomic planes
The atoms in a crystal are a periodic array of coherent scatterers and
thus can diffract light.
•Diffraction occurs when each object in a periodic array scatters
radiation coherently, producing concerted constructive interference at
specific angles.

•The electrons in an atom coherently scatter light.

•Atoms in a crystal form a periodic array of coherent scatterers.

–The wavelength of X rays are similar to the distance between atoms.

–Diffraction from different planes of atoms produces a diffraction

pattern, which contains information about the atomic arrangement
within the crystal 10
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Scattering of X-ray by atomic planes

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Scattering of X-ray by atomic planes

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BRAGG’s law
• Consider crystals as built up in layers or planes such that each acts
as a semi-transparent mirror.
• Some of the X-rays are reflected off a plane with the angle of
reflection equal to the angle of incidence, but rest are transmitted
to be subsequently reflected by succeeding planes
1 Deviation = 2 1’

2 2’
  A
d x d  z d
B
y
d d
C 13
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BRAGG’s law
• Two X-ray beams, 1, and 2 are reflected from adjacent planes, A and
B, within the crystal and our aim is to know under what condition the
reflected beams 1’ and 2’ are in phase.
• Beam 22’ has to travel the extra distance xyz as compared to beam
11’ and for 1’ and 2’ to be in phase, distance xyz must equal to a
whole number of wavelengths.
• The perpendicular distance between pairs of adjacent planes, the d-
spacing, d, and the angle of incidence, or brag angle θ are related to
the distance xy by
xy = yz = d sinθ
xy+yz = xyz = 2d sinθ
But, xyz = nλ
Therefore;

 For constructive interference: 2d Sin = n 14

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BRAGG’s law cont.
Bragg’s law: 2d Sin = n
 n is an integer and is the order of the reflection
 For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å

n Sin 
1 0.34 20.7 First order reflection from (110)
Second order reflection from
2 0.69 43.92 (110)
Also written as (220)
a
d hkl 
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h k l
2 2 2
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Lattice planes, Miller indices
These are labels for the planes of atoms in the lattice
Each set of Miller planes gives rise to a peak in the diffraction pattern
whose diffraction angle is related to the d-spacing by the Bragg
equation
Take the reciprocal of the fractional intercepts on each axis and write in
round brackets i.e. - 1/2a, 1/2b, 1/2c ---- (222) plane
(100), (010), (001) define a, b and c axes

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Lattice planes, Miller indices
Step 1: Identify the intercepts on the x- , y- and z- axes.

Step 2: Specify the intercepts in fractional co-ordinates.

Step 3: Take the reciprocals of the fractional intercepts.

Step 4: Clear fractions.

If the x-, y-, and z- intercepts are 2, 1, and 3, the Miller Indices are
calculated as (362)
How to locate a direction:
Example: [231] direction would be 1/2 intercept on cell a-length 1/3
intercept on cell b-length and 1 intercept on cell c-length
Directions are always denoted with [xyz]
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Miller indices
Find out miller indices:
1. Intercept length in x, y and z directions are 1, 1, 1 (111)
2. Intercept length in x, y and z direc ons are 1, 1, ∞ (110)
3. Intercept length in x, y and z direc ons are 1, ∞, 1/2 (102)

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Miller indices
(001) (100) (010)

(101) (110) (011)

(212)
(301)

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Primitive and Non-Primitive
Lattice
A unit cell which contains one lattice point is called a primitive unit cell.
In a proimitive unit cell, constituent particles are present only at the
corners of a unit cell.

A non-primitive unit cell, the constituent particles are present not only
at the corner, but also in centres of a face and body of the unit cell.

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Lattice

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BRAGG’s law cont.

n Sin 
1 0.34 First order reflection from (110)
Second order reflection from (110)
2 0.69 43.92°
Also written as (220)

Calculate the ratio of lattice spacing of 110 and 220

a
d hkl 
h k l
2 2 2
d 220 
a
8 d 220 1

a d110 2
d110 
2

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The powder method

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Conclusions
 Monochromatic X-Ray
 Scattering of X-ray by an atom
 BRAGG’s law
 Lattice planes, Miller indices
 Primitive and Non-Primitive Lattice
Next Class
 Extinction Rules for different Bravais lattices
 Allowed reflection planes
 Crystal structure determination
 Lattice strain: Effect

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