Unit II

Chapter 1
CRYSTALLOGRAPHY
Introduction:

Solid:

 It is one of the states of matter in which large number of atoms or molecules or

ions are closely packed together.
 The physical structure of a solid and its properties related to the arrangement of
atoms or molecules or ions within it.

Crystallography:
 The word "crystallography" derives from the Greek words krystallon = clear ice,
and graphine= write
 The study of the geometrical form (i.e., arrangement of atoms in solids) and other
physical properties of solids by using X-Rays, electron beams and neutron beams
etc. is termed as the science of crystallography.

Classification of solids:
Every solid element has its own internal structure. The internal structure of solid depends
on the internal arrangement of atoms or molecules or ions.
Solid are classified in two categories based on the internal arrangement of atoms or
molecules.
1. Crystalline solid or crystals and
2. Amorphous solids or no-crystalline solid.

1. Crystalline solids or crystals:

Solids that have a definite shape and size are called crystalline solids.
Properties of crystalline solids:
 In Crystal solids, the atoms or molecules are arranged in a regular and periodically
in three-dimensional manner.
 If the crystal breaks, the broken pieces also have regular shape.
 They have characteristic geometrical shape.
 Some crystalline solids are anisotropic i.e. the physical properties like thermal
conductivity, electrical conductivity, refractive index and mechanical strength of
crystalline solids are different along different directions.
 Melting point of crystalline solids is extremely sharp. Because, when the
temperature increases, bonds break at the same time. This is due to the strength of
all the bonds between different atoms, molecules and ions is equal.
 They are most stable as compared to other solids.
 Examples: i. Metallic crystals: Gold, Silver, Aluminum, etc.
ii. None-metallic crystals: Diamond, Silicon, Germanium, and Sodium
chloride etc.
Amorphous solids or Non-crystalline solids:
Solids that have no particular external shape are known as amorphous solids.
The word amorphous comes from the Greek a means without, and morphé, means shape
or form.
Properties of Amorphous solids:
 In amorphous solids, the atoms or molecules are arranged in an irregular manner.
 If an amorphous solid breaks, the broken pieces are irregular in shape.
 They do not have sharp melting points. This is due to the variable strength of
bonds present between the molecules, ions or atoms. So, bonds having low
strength on heating break at once. But the strong bonds take some time to break.
 They are isotropic in nature. Isotropic means that in all the directions their
physical properties will remain same.
 They are less stable.
 Example Glasses, plastics, Rubbers etc.

1. Crystal lattice (or) Space lattice

A crystal structure can be studied in terms of an idealized (imaginary) geometrical
concept is called a space lattice and is introduced by Auguste Bravias in 1848.
According to this concept,
 Each atom in the crystal structure can be replaced by a point in space .These points are
known as lattice points.
 A Geometrical representation of the crystal structure in terms of lattice points in three
dimensional space is called “space lattice (or) crystal lattice”.
 Lattice points are arranged in regular and periodically in three-dimensional order in
space. In which every lattice point has the same environment with respect to all other
points.
 Lattice points denote the position of atoms (or) molecules or ions in the crystal
(fig.1)
 It is an imaginary concept.

Lattice
2. Basis (or) motif:

 A Group of atoms or molecules or ions is called ‘Basis’

 Basis may consist of single atom or a group of atoms.

(a) Single atom (b) Di atomic molecule (c) Tri atomic molecule (d) Ion

Crystal structure:
 Crystal structure is a combination of lattice and basis.
 A crystal structure is formed by adding basis (atoms) to every lattice point of the
space lattice. The number of atoms in the basis may be one or more than one.
 Thus the crystal structure is real and the crystal lattice is imaginary
 The logical relation is Crystal structure = Space lattice + basis.

3. Unit cell:

 Crystal structure can be defined in terms of unit cell.

 The unit cell is the smallest block or geometric figure of crystal, from which the
entire crystal is built up by repetition in three dimensional manners.
 It represents the actual structure of crystal.
 The three dimensional representation of unit cell is as shown in figure.
Fig. Unit cell in 2D -space lattice Fig. Unit cell in 3D -space lattice
Types of unit cells:
There are two distinct types of unit cells: primitive and non-primitive.

1. Primitive cell:
 A primitive cell is the simplest type of unit cell which contains only one lattice
point per unit cell (contains lattice points at its corner only).
 Primitive unit cells contain only one lattice point, which is made up from the
lattice points at each of the corners.
Ex: Simple cubic (SC)

Fig: Simple Cube

2. Non-primitive cell:
 If there are more than one lattice points in a unit cell, it is called a Non-primitive
cell.
 Non-primitive unit cells contain additional lattice points, either on a face of the
unit cell or within the unit cell, and so have more than one lattice point per unit
[Link]: BCC and FCC contain more than one lattice point per unit cell

(a) BCC (b) FCC

Lattice parameters of unit cell:
Definition:

To represent a lattice unit cell, we require the six parameters i.e., Axial lengths (a,b,c) and
interfacial angles (α,β,γ) these quantities are known as “Lattice Parameters”.
i.e., Lattice parameters are
1. Axial lengths (a,b,c)
2. Interfacial angles (α, β, γ)

Explanation:

Consider a cubic unit cell with crystallographic

axes X, Y, Z as shown in figure.
Let OA=a, OB=b, and OC=c be the intercepts
made by the unit cell along the crystallographic
axes. These quantities a, b and c are called
translational vectors (or) axial lengths or
primitives.
The angles between the three crystallographic axes
are known as interfacial angles.
The angle between a and b is alpha (α) and b and
c, is beta (β), and that between a and c is gamma
(γ).
These three angles (α, β, γ) are called interfacial
angles.

The crystal systems and Bravias lattices:

Crystals are classified into 7 crystal systems on the basis of lattice parameters viz:
(i) Axial lengths a,b,c and
(ii) Interfacial (axial) angles α,β,γ.

The 7 basic crystal systems are

1. Cubic
2. Tetragonal
3. Orthorhombic
4. Monoclinic
5. Triclinic
6. Rhombohedral OR Trigonal
7. Hexagonal

Bravais Lattices:

Bravais in 1880 showed that there are 14 possible types of space lattices in the 7 crystal
systems as shown in table.
According to Bravais, there are only 14 possible ways of arranging points in space lattice
from the 7 crystal systems .Theses 14 space lattices are called the Bravais lattices.

The possible types of Bravias lattices are four and following names and symbols
represent them,

Primitive lattice-P, Body centered lattice-I, Face centered lattice-F, and Base centered
lattice-C.
 In the simple primitive lattice (P), the lattice points are situated only at the corners
of the unit cell.

 In the body- centered lattice-I (I - from the German "Innenzentriert” means inner
centered), the lattice points are situated at the corners and also at the intersection
of the diagonals (centre) of the unit cell.

 In the face- centered lattice-F (F- from the German "Flächenzentriert” means
face centered), the lattice points are lie at the corners and also at the centers of all
the six faces of the unit cell.

 In the base- centered lattice (C), the lattice points are lie at the corners as well as
at the centers of the unit cell, which are opposite to each other.
Name Axial lengths Interfacial angels [Link] Bravias
Bravias lattice
lattices

[Link] a=b=c α = β = γ = 90° 3 P, I ,F

[Link] a=b≠c α = β = γ = 90° 2 P, I

P, I, F,
[Link] a≠b≠c α = β = γ = 90° 4
Base

[Link] a≠b≠c α = β = 90° ≠ γ 2 P, Base

[Link] a≠b≠c α ≠ β ≠ γ ≠ 90° 1 P

[Link] a = b = c α = β = γ ≠ 90° 1 P

α = β = 90°, γ =
[Link] a=b≠c 1 P
120°

The 7 crystal systems and Bravias lattices are discussed briefly one by one as follows
1. Cubic crystal system:
In cubic crystal system, the three crystal axes perpendicular to each other and axial
lengths are the same along the entire three axes as shown fig.
Lattice parameters:

All three sides equal, a=b=c

All three right angles, α= β= γ=900

Examples: Pb, Hg, Ag, Po, Au, Cu, ZnS, diamond, KCI, CsCl ,
NaCl, Cu2O, CaF2 and alums etc.

Possible Bravais lattices:

Fig: cubic system
 Primitive
 Body centered
 Face centered.
 Fig: Possible Bravias lattices of cubic system

2. Tetragonal System:
In tetragonal system, the three crystal axes are perpendicular to each
other. Two of the three axis lengths are the same, but the third length
is different, as shown in fig

Lattice parameters:

 Two sides equal , a=b ≠c

 All three right angles; α= β= γ=900

Fig: Tetragonal
Examples: system
Niso4
Sno2 and
Indium
Possible Bravais lattices:

 Primitive
 Body centered

Fig: Possible Bravias lattices of tetragonal system

3. Orthorhombic Crystal System:

In orthorhombic crystal system, the crystal axes are perpendicular to each other and all the
three axial lengths are of unequal lengths (different), as shown in fig.
Lattice parameters:

 All the sides different a≠b≠c

 All three right angles; α= β= γ=900

Examples: KNO3, Baso4and Mgso4 etc

Possible Bravais lattices:

 Primitive Fig: Orthorhombic
 Body centered System
 Base centered
 Face centered.

Fig: Possible Bravias lattices of orthorhombic system

4. Monoclinic Crystal system:

In monoclinic crystal system, two of the crystal axes perpendicular to each other, but the
third obliquely inclined. The three axial lengths are different along the axes as shown in
Fig.
Lattice Parameters:
 All the sides different a≠b≠c
 Two right angles, third arbitrary α=β=900, γ ≠900

Examples: Na2sO4, Feso4 , No2So3 etc

Possible Bravais lattices:

 Primitive Fig: Monoclinic system
 Base centered

Fig: Possible Bravias lattice of monoclinic system

5. Triclinic crystal system:
In triclinic crystal system, all the three crystal axes are not
perpendicular to each other. The axial lengths are also not equal
(different) along the three axis, as shown in fig.
Lattice parameters:

 All three sides different a≠b≠c

 All three angles different α≠ β ≠ γ≠900

Examples: Cuso4 and k2cr2o7

Possible Bravais lattices: Fig: Triclinic system

 Primitive

Fig: Possible Bravias lattice of triclinic system

6. Trigonal (Rhombohendral) crystal system:

In trigonal crystal system, the three axes are inclined to each other at an
angle other 900. The three axial lengths are equal along three axes as shown
in fig.
Lattice parameters:
 All the sides equal a=b=c
 All three angles equal, of arbitrary value α=β≠900

Examples: Caso4, Bi, Sb, calcite etc.

Possible Bravais lattice:

 Primitive

Fig: Trigonal system

Fig: Possible Bravias lattice of Rhombohedral system

7. Hexagonal system:
In hexagonal crystal system, two of the crystal axes are 900 apart, while
the third is perpendicular to both of them.
The axial lengths are the same along three axes that are 900 apart, but
the axial length along the third axis is different as shown in figure.

Lattice parameters:

 Two sides equal, third arbitrary a=b≠c

 Two right angles, third angles 1200, α=β=900 ; γ=1200
Fig: Hexagonal system
Examples: Tourmaline, Quartz, AgI and Sio2

Possible Bravais lattices:

 Primitive

Fig: possible Bravias lattice of hexagonal system

Structures of cubic system:

There are three types of structures possible in this
system depending on the position of the lattice point
(atoms) in the unit cell fig.
(1) Simple cubic (sc) (or) primitive
(2) Body centered cubic (BCC) and
(3) Face centered cubic (FCC)

1. Simple cubic (SC) crystal structure:

 In this structure; there are only 8 atoms one
at each corner of the cube.
 The corner atoms touch each other along the
edges as shown in fig.
 Each and every corner atom is shared by 8
adjacent unit cells.
(2) Body-centered cubic structure (BCC)

 In this case, we have two types of atoms

fig,(i) Corner atoms and (ii) Body centered
atoms i.e., there are 8 corner atoms, one at
each corner of the unit cell and one body
centered atom at the centre of the unit cell as
shown in fig.
 In this structure, the corner atoms do not
touch each other. But each corner atom
touches the body centered atom along the
body diagonal as shown in fig.
 Each and every corner atom is shared by 8
adjacent unit cells and the body centered atom
is shared by that particular unit cell alone and
is not shared by any other unit cell.

(3) Face-centered cubic structure (FCC):

 In this case, we have two types of atoms viz (i) Corner atoms and (ii) Face
centered atoms, i.e. there are 8 corner atoms, one at each corner of the unit cell
and six atoms at the centers of six faces of unit cell as shown in Fig.
 In this structure, the corner atoms do not touch each other. But each corner atom
touches the face centered atoms along the diagonal of the face of the cube as
shown in fig.
 Each and every corner atom is shared by adjacent unit cells, and each face
centered atom is shared by only two unit cell, which lie on either side of the atom.
 Fig: Face-centered cubic structure (FCC):

Coordination Number:
Definition:
Coordination Number is the number of nearest neighboring atoms to a particular atom
which are direct contact with each other.
The Coordination Number for the three types of cubic crystal structure can be calculated
as follows.
(a).Simple Cubic Structure:
 In this case, there are only 8 atoms, one at each corner of the cube (or) unit cell.
For a particular atom say ‘C’ atom, there are 4 nearest neighboring atoms, i.e.
atoms 1,2,3 and 4 on its own plane and there are 2 more nearest atoms i.e., atom-5
directly above the plane and atom-6 directly below the plane as shown in figure.
 Therefore,The total Number of neighboring atoms to particular atom (C)
=4+1+1=6

Hence, the coordination for SC =6

Fig: Co- ordination number in Simple cubic structure

(b). Body centered cubic Structure:

 In this case, we have two types of atoms namely

[Link] atoms 2. Body centered atoms i.e., there
are 8 corner atoms, one at each corner of the unit cell
and one body centered atom at the center of the unit
cell as shown in figure.
 The corner atoms do not touch each other. But each
corner atom touches the body centered along the
body diagonal. Thus for particular atom ‘C’ at the
body centre obviously, there are 8 nearest neighbor
(corner atoms).
Hence, the coordination for BCC =8

Fig: Co- ordination number in BCC

(C). Face Centered Cubic Structure (FCC):

 In this case, we have 2 types of atoms namely,

[Link] atoms and 2. Face centered atoms.
There are 8 corner atoms, one at each corner of
the unit cell and six atoms at the centers of six
faces of unit cells as shown in figure.
 Let us consider 2 unit cells one above the other if
the reference atom ‘C’ taken as the face centered
atom then it is surrounded by 4 corner atoms on
the plane , and 4-face centered atoms above the
plane and 4-face centered atoms below the plane
as shown figure.
 Therefore the coordination number for
FCC=4+4+4=12

Fig: Co- ordination number in FCC

Atomic packing factor (APF) or packing density:

Definition:
Atomic packing factor is defined as the ratio of the volume occupied by the total number
of atoms per unit cell to the total volume occupied by the unit cell.

i.e., APF = = v/V

The packing factor (or) packing density of the three cubic systems can be calculated as
follows.
 (a).Simple cubic structure (SC):
In simple cubic,
The number of atoms per unit cell=1
Volume of 1 atom (spherical) = r3

Volume occupied by the total no. of atoms per unit cell (v)
= No. of atoms per unit cell x volume of one atom
= 1x r3
We know the radius of atom in simple cubic r =

=1x ( )3

Volume of the unit cell (V) = length x breadth x height

We know that for a cubic system, length=breath=height=a
V=a x a x a
= a3

A.P.F = v/V =

= = 0.52

APF = = 0.52

And Void space = (1-APF) x 100

= (1-0.052) x 100
=48%

Therefore, we can say that 52% volume of the unit cell of sc is occupied by atoms and
remaining 48% volume is vacant. Thus, the packing density 52%
Since the packing density is very low, SC has loosely packed structure.

(b)Body-centered cubic Structure:

In body-centered cubic structure,

The number of atoms per unit cell=2
Volume of one atom (spherical) = r3
Volume occupied by the total no. of atoms per unit cell =
[Link] atoms per unit cell x Volume of one atom
=2 x r3

3
=2 x [a
 = [ ]

v = a3

Volume of the unit cell for a cubic system (V) =a3

APF = = a3 /a3

0.68

APF= =0.68

And Void space = (1-APF) x 100

= (1-0.068) x 100
=32%

Therefore, we can say that 68% volume of the unit cell of BCC is occupied by atoms and
remaining 32% volume is vacant. Thus, the packing density 68%.
Since the packing density is very low, SC has loosely packed structure.

(C) Face-centered cubic structure:

In face centered cubic structure,

The number of atoms per unit cell=4
Volume of one atom (spherical) = r3
Volume occupied by the total [Link] atoms per unit cell (V) =[Link] atoms
perunit cell x volume of one atom

4x r3
We know that the radius of atom in FCC is r =

V=4x ( )3

= a3 /6

Volume of the unit cell for a cubic system (V) =a3

APF = =

=
 =0.74

APF= =0.74

And Void space = (1-APF) x 100

= (1-0.074) x 100
=26%

Therefore, we can say that 74% volume of the unit cell of FCC is occupied by atoms and
remaining 26% volume is vacant. Thus, the packing density 74%
Since the packing density is very high, FCC has closely packed structure.

Miller indices:
 Miller introduced to a set of three numbers to designate plane in a crystal. This set of
three numbers is known as Miller indices of the concerned plane and is denoted by
(h k l).
 Miller indices are the reciprocals of the intercepts made by the plane along the three
crystallographic axes which are reduced to smallest numbers.
Produce for finding Miller indices :
1. Find the intercepts made by the plane along the three crystallographic axes.
2. Express the intercepts in terms of multiples of axial lengths.
3. Find the reciprocal of the numerical intercept values.
4. Convert these reciprocals into whole numbers by multiplying each with their
LCM.
5. Enclose these numbers in bracket ( ).This represents the Miller indices of
the concerned plane
Example:
Step 1: Find the intercepts made by the plane along the three crystallographic axes
(p, q, r).
Let us consider the plane ABC along the three axes X, Y, and Z, which cuts 1-
unit along the X-axis, 2-units along the Y-axis and 3-units along the Z-axis as shown in
fig.
From fig; Intercepts p = 1, q =2 and r =3

Step2: Express the intercepts in terms of multiples of axial lengths

(pa, qb, rc).
From fig; Pa: qb: rc
1a: 2b: 3c

Where p = 1, q =2 and r =3

Step 3: Find the reciprocal of the numerical intercept values ( )

Step4: Convert these reciprocals into whole numbers by multiplying each with their
LCM.
X6
[Link]
Step5: Enclose these numbers in bracket (6 3 2). This represents the Miller indices of
the concerned plane

Interplaner distance or spacing (d):

(Saperation between Successive (hkl) Planes)
The separation between two successive or adjacent lattice planes is called interplaner
distance or spacing and it is denoted by‘d’.
Determination of Interplaner distance between two successive Planes.
 Consider two successive lattice planes ABC and AIBICI in a cubic unit cell as
shown in fig 1.
 Let ON = d1 be the perpendicular distance or normal
between the origin (O) and the first plane ABC.
 Let OM = d2 be the perpendicular distance or normal
between the origin (O) and the first plane ABC and
 Let MN =d be the interplaner distance between two
planes ABC AND AIBICI.

i.e., MN = OM-ON
d = d2- d1

Fig: Planes in a cubic unit cell

Calculation of d1:

 Let us consider the plane ABC as shown in fig.

 Let ON = d1 be the perpendicular distance or normal
between the origin (O) and the first plane ABC.
 Let α, β and γ be the angles between ON and X,Y,and Z
axes respectively .
 Let OA = , OB = and OC = be the intercepts made
by the orthogonal axis OX, OY and OZ.

 From ONA
Cos = = = (1)
  From ONB
Cos = = = (2)

 From ONC
Cos = = = (3)

According to the law of directions of cosine law

Cos2 + Cos2 +Cos2 =1 (4)
Substituting equations (1) (2) & (3) in equation (4)

For cubic system a=b=c;

=1

= (5)
This is the perpendicular distance from origin to the first plane.
Calculation of d2:
 Let us consider the plane AIBICI as shown in fig.
 Let OM = d2 be the perpendicular distance or normal between the origin (O) and
the first plane AIBICI.
 Let αI, βI and γI be the angles between ON and X,Y,and Z axes
respectively .
 Let OAI = , OBI = and OCI = be the intercepts made by
the orthogonal axis OX, OY and OZ.
 From fig, the perpendicular distance from origin to the second
plane
Can be calculated as

= (6)

 Therefore, the interplaner distance between two planes ABC AND AIBICI is

d = d2-d1
 d=

d=

The above equation represents the interplaner distance between any two successive planes
in a cubic crystal.
 Chapter 2
X-RAY DIFFRACTION
X-ray diffraction:

 Like light rays X-rays also exhibit diffraction phenomena when they passes
through the crystals.
 The bending of X-rays around the obstacle. X-rays are mostly used to study the
crystal structures because the wavelength of X-rays (~ 1Å) is comparable with the
interatomic distance or spacing. This was first discovered by the German physicist
Max von Laue in 1912.
 According to Max von Laue, a crystal serves as a natural three dimensional
grating for X-rays, where the regular and periodically in three-dimensionally
arrangement of atoms or molecule or ions act as the parallel lines or grating
elements in the 2D optical grating.
 His associates, [Link] and [Link] proved experimentally that X-rays are
waves and that the atoms/molecules/ions in a crystal are arranged in regular
manner.
 In the same year, [Link] and [Link] derived a relation between the
wavelength of X-rays, angle of diffraction and separation of atomic planes in the
crystal called Braggs law.
Bragg’s law:
 Consider a crystal which consists of equidistant parallel planes with the
interplanar spacing ‘d’ as shown in figure.
 When X-rays of wavelength ‘’ fall on these crystal planes, the atoms in the
planes diffract the x-rays in all directions.
 Let the X-ray PA incident at an angle ‘θ’ with the plane I be reflected at atom A
in the direction AR and another X-ray QC reflected at atom C in the direction CS.
These diffracted X-rays will interfere constructively or destructively depending on
the path difference between X-rays.
 To calculate the path difference, two normals AB and AD are drawn from A to
QC and CS.
 Path difference = BD
= BC+CD ----------(1)
From ∆ABC,

Sinθ =

CB =AC sinθ
CB = d Sinθ ------------(2)
Similarly from ∆ACD ,

Sinθ =

CD = AC Sinθ
CD = d Sinθ ----------------(3)
From (1), (2) & (3) we have,
Path difference = d Sinθ + d Sinθ
Path difference = 2 d Sinθ --------------(4)

To get maximum intensity, path difference should be equal to integral multiple of  .

Path difference = n ------------------------(5)

From (4) and (5) we have,

2 d Sinθ = n -------------(6)

The above expression represents Bragg’s law.

Importance:
 From the Bragg’s Law

d =
Knowing the values of the wavelength of X-rays(λ) and angle of diffraction( ,
separation of atomic planes(d) can be calculated.
 Knowing the value of d, lattice constant ‘a’ of the cubic crystal can be calculated.
 For cubic crystal; d =
Knowing the value of d, lattice constant ‘a’, values of h2 + k2 + l2 can be calculated and
we can classify the SC, BCC and FCC crystal systems.
Bragg's X-Ray Diffractometer

The schematic arrangement of Bragg's spectrometer is shown in Figure (a). X-ray

from the X-ray tube is narrowed to obtain a fine pencil of the beam by passing them
through slits S1 andS2 provided in lead screens. The beam is now allowed to fall on a
crystal ‘C’ (usually of NaCl with 100 face) mounted on a circular turn table of the
spectrometer. This turn table is capable of rotation about a vertical axis passing through
its centre. The rotation can be read on a circular graduated scale ‘S’ with the help of
vernier ‘V1’.

The reflected beam then passes through slits S3 and enters the ionisation chamber.
The ionisation chamber is simply a container for gas or vapour with two electrodes. The
ionisation chamber is mounted on a special movable arm about the same axis of crystal.
The position of ionisation chamber can be read by a second vernier V2. The turn table and
ionisation chamber are linked together in such a way that when the turn table rotates
through an angle ‘θ’, the ionisation chamber turns through 2θ.
In this way, the beam is always reflected into the ionisation chamber, whatever the
glancing angle at the surface of the crystal. The X-rays entering the ionisation chamber
ionise the gas which causes a current to flow between two electrodes which can be
measured by galvanometer ‘G’.
The ionisation current is measured for different values of glancing angle ‘θ’. A
plot is then obtained between‘θ’ and the ionisation current. The graph is shown in fig. (b).
For certain values of glancing angle ‘θ’, the intensity of the ionisation current increases
abruptly. We know from the Bragg's equation that 2d sinθ = nλ
For the first-order spectrum n = 1and 2dsinθ1 = λ
For the second-order spectrum n =2 and 2dsinθ2 = 2λ

For the third-order spectrum n =3 and 2dsinθ3 = 3λ

sinθ1: sinθ2 : sinθ3 = 1 : 2: 3
From the graph of glancing angle ‘θ’ and ionisation
current [fig. (b)], the glancing angles θ1, θ2, θ3 for first,
second and third order reflections are measured. It can be
seen that
sinθ1: sinθ2 :sinθ3 = [Link]. This shows that the assumption
that X-rays get reflected like ordinary light is justified. Here
we have assumed that the X-ray beam is monochromatic.
Fig. 11(c) represents the case when X-ray beam consists
of two wavelengths ‘λ1’ and ‘λ2’. In this case, peak values
like A1, B1; A2, B2; and A3, B3 are obtained. The peak
values A1, A2, A3 are corresponding to wavelength ‘λ1’
while peak values B1, B2, B3 are corresponding to
wavelength ‘λ2’. It is observed that Bragg's equation
sinθ1: sinθ2 :sinθ3 = [Link] is satisfied. Similarly, if
are glancing angles for wavelength ‘λ2’, it is
again observed that Bragg's equation
is satisfied.
From the observed value of ‘θ’ and known values of ‘d’
and ‘n’, the wavelength λ of X-ray can be calculated by using Bragg's equation, i.e., 2d
sinθ = nλ
The following facts are observed:
(i) As the order of spectrum increases, the intensity of the reflected X-rays decreases.
(ii) The ionisation current does not fall to zero for any value of glancing angle ‘θ’. It is
maximum for certain angles. This shows the existence of a continuous spectrum over
which the characteristic line spectrum is superposed.

Crystal structure determination:

1. Laue Method
2. The Powder Method (or) Debye –Scherrer Method

Laue Method:
The laue method is one of the X-ray diffraction techniques used for crystal structure
studies. The experimental arrangement is shown in figure below.
The crystal whose structure has to be studies, is held stationary in a continuous X-
ray beam .After passing through the pin holes of lead diaphragms, we obtain a fine beam
of X-rays. These X-rays are allowed to fall on the crystal. The crystal planes in the crystal
diffract the X-rays satisfying Bragg’s law.

Figure : 1 Laue Method

 The diffracted X-rays are allowed to fall on a photographic plate. The diffraction
pattern consists of a series of bright spots corresponding to interference maximum for a
set of crystal planes satisfying the Bragg’s equation 2dsinθ = nλ for a particular
wavelength of incident beam.
The distribution of spots depends on the symmetry of the crystal and its orientation
with respect to X-ray beam .For a simple cubic crystal, the Laue photograph is shown in
below figure

Figure : 2 Laue photograph of simple cubic crystal

The Powder Method (or) Debye –Scherrer Method:

The powder diffraction method was devised independently in 1916 by Debye and
Scherrer in Germany and in 1917 by Hull in the United States.
This method is used to study the structure of the polycrystalline solids in the form
of a fine powder, containg a large number of tiny crystallites with random orientations.
The experimental arrangement of Debye- Scherrer method is shown in fig.
 Fig : Photographic Film

 It consists of a source(S) of X-rays.

 The beam of X-rays is monochromatised by passing through a filter and
collimated by passing through a collimator.
 The collimator produces collimated beam and falls on the powder sample or
specimen.
 The powder sample or specimen is taken a thin walled non diffracting capillary
tube.
 The specimen is placed in the Debye-Scherrer camera and the photographic film is
mounted or located round the inner surface of the camera covering nearly the
whole circumference in order to receive the beams diffracted up to 1800.
 The specimen is suspended vertically on the axis of a Debye-Scherrer camera.
 The collimated X-rays beam passing through the entry hole and falls on the
powdered specimen, since crystallites with random orientations, almost all the
possible and d values are available for diffraction of X-rays.
 The diffraction takes places for the values of and d which satisfies the Braggs
condition, i.e., 2dsin = n λ.
 The diffracted X-rays come out through the exit hole in the form of a cone.
 The diffracted X-ray cones make impressions on the film in the form of arcs on
either side of the exit and entry holes with their centers coinciding with the holes.
 The film is exposed for a few hours in order to obtain arcs of sufficiently high
intensity.
 It is than removed from the camera and developed.
 The arcs are produced on the developed film appear dark, as shown in fig.
 From fig ; the angle corresponding to a particular pair of arcs is given by
4 (radians) = (since, angle = )
Where S is the arc length (i.e., distance between two arcs) and
R is the radius of the camera.
4 (degress) = ( )=
From the above expression, can be calculated.
Hence, knowing the values of and λ, the inter planer distance d for a set of
parallel planes can be calculated using the Braggs condition.
d=
These d values are used to find the space lattice of the crystal structure.