UNIT-II
CRYSTALLOGRAPHY AND X-RAY DIFFRACTION
Crystal Physics’ or ‘Crystallography’: is a branch of physics that deals with the
study of all possible types of crystals and the physical properties of crystalline solids by the
determination of their actual structure by using X-rays, neutron beams and electron beams.
Solids consists of large number of closely packed atoms or
molecules. Solids are classified into two types based on their
arrangement of atoms or molecules.
1. Crystalline Solids
2. Amorphous Solids
Crystalline Solids: If the atoms or molecules in a solid are
arrange In a regular or periodic manner. Then the solids are
said to be crystalline Solids.
They process long range order of atoms.
It has regular shape and when it is broken, all broken pieces have the same regular shape.
It has sharp melting point.
They are Anisotropic in nature I.e., physical properties (like mechanical, optical and electrical
etc) have different values in different direction.
they do not have melting point.
It may be made up of metallic crystals or non-metallic crystals.
Examples: Cu, Al, W, Mg,
Carbon, crystalized
polymer and plastics.
crystalline Solids are of two types.
They are 1. Single Crystal solids
2. Polycrystalline solids
1) Single Crystaline solids: If the
periodic arrangement atoms or molecules are extended to the entire crystal is said to be single
crystalline solids. Examples: Cu, Al, Cu etc.,
2. Polycrystalline solids: If the arrangement of atoms or molecules are extended to small reasons
known as grains and combination of such grains known as polycrystalline solids.
Examples: Quartz, calcite, sugar, mica, diamonds, snowflakes, rock, calcium fluoride, silicon
dioxide, and alum, NaCl.
Amorphous solids: If the atoms or molecules in a solid are arranged In irregular manner. Then the
solids are said to be Amorphous Solids.
Examples: Glass and Rubber
They process short range order of atoms.
They do not possess any regular shape.
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They are isotropic in nature I.e., physical properties (like mechanical, optical and electrical
etc) have same values in different direction.
they do not have sharp melting point.
CRYSTAL LATTICE or SPACE LATTICE: It is defined as an infinite array of points in three dimensions in
which every lattice point has identical surrounding.
SPACE LATTICE crystal structure
Fig:2D SPACE LATTICE
Basis: A crystal structure is formed by associating every lattice point with an unit assembly
of atoms or molecules identical in composition, arrangement and orientation. This unit
assembly is called the `basis’.
When the basis is repeated with three directions, it gives the actual crystal structure.
SPACE LATTICE+ Basis = crystal structure
UNIT CELL: Unit cell is the smallest geometric figure of the crystal lattice when it is
repeated in three dimensions.
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CRYSTALLOGRAPHIC AXES:
Consider a unit cell consisting of three
mutually perpendicular edges OA, OB and
OC as shown in figure.
Draw parallel lines along the three edges.
These lines are taken as crystallographic
axes and they are denoted as X, Y and Z
axes.
LATTICE PARAMETERS:
Consider the unit cell as shown in
figure(b).
Let OA, OB and OC are the intercepts made by the unit cell along X, Y and Z axes
respectively.
These intercepts are known as primitives. In crystallography the intercepts OA, OB and OC
are represented as a, b and c.
The angle between X and Y axes is represented as . Similarly, the angles between
Y and Z and Z and X axes are denoted by and respectively as shown in the above
figure.
These angles, and are called as interaxial angles or interfacial angles.
To represent a lattice, the three interfacial angles and their corresponding three intercepts
are essential. These six parameters are said to be lattice parameters.
PRIMITIVE CELL: It is the smallest unit cell in volume
constructed by primitives. It consists of only one full
atom. A primitive cell is one, which has got the points or
atoms only at the corners of the unit cell. If a unit cell
consists of more than one atom, then it is not a primitive
cell. Example for primitive cell: Simple Cubic unit cell.
Examples for non-primitive cell: BCC and FCC unit cell
Seven Crystal Systems:
The crystal classified into seven types, based on the on the basis of the shape of the unit cell or
lattice parameters. They are 1. Cubic 2. Tetragonal 3. Orthorhombic 4. Trigonal (rhombohedral) 5.
Hexagonal 6. Monoclinic and 7. Triclinic
[Link]. Crystal system Axial length Interfacial angles Example
1. Cubic a=b=c === 90° NaCl, CaF2, Au, Cu
2. Tetragonal a=bc === 90° tin, Indium, SnO2
3. Orthorhombic abc === 90° Sulphur, Topaz, BaSO4, KNO3
4. Monoclinic abc = = 90°; 90° Na2So4, FeSo4, Gypsum
5. Triclinic abc 90° CuSo4, K2Cr2O7
6. Rhombohedral a=b=c = = 90° Calcite, Sb, Bi.
7. Hexagonal a=bc ==90°;=120° Quartz, Zn, Mg.
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BRAVAIS LATTICES: -
There are 14 bravais lattice in 3 dimensions. Each of these 14 Bravais lattice belongs to 7 crystal
system.
Lattice symbol:
1) ‘P’:- Primitive or Simple cell: It has lattice points at corners only.
2) ‘C’:- Base centered cell: It has an extra atom at the center of base only.
3) ‘I’:- Body centered cell: It has an extra atom at the center of body.
4) ‘F’:- Face centered cell : It has extra atoms at the centers of all six faces.
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Properties of the Unit cell (Cubic)
1. Volume of a unit cell:
If a,b,c,, and are called lattice parameters.
For cubic system a=b=c and ===90 0 .
Therefore V= a3 .
2. Co-ordination number: the number of equidistant neighbours that an atom has in a crystal
lattice is known as co-ordination number.
The co-ordination number for an atom in simple cubic structure is = 6 .
The co-ordination number for an atom in body centred cubic structure is =8 .
The co-ordination number for an atom in face centred cubic structure is =12
3. Number of atoms per unit cell is the number of atoms In a unit cell by considering contribution
of corner atoms, centre atoms and face centred atoms.
An atom situated at the corner share 1/8 th part to a unit cell.
An atom situated at the face share 1/2 part to a unit cell.
An atom situated at the canter of the body share one full part to a unit cell.
[Link] neighbouring distance(2r): the distance between two nearest neighbouring
atoms in a crystal lattice is called Nearest neighbouring distance.
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[Link] packing factor (APF) or or packing density or density of packing:
Atomic packing factor is defined as the ratio between the volumes occupied by the
total number of atoms per unit cell (v) to the total volume of the unit cell (V).
Cubic Crystal structures:-
1) Simple Cubic (SC) structure:-
Each corner atom surrounded by 6 equidistant atoms. So co-ordination number is 6.
Here atoms are present at corners of the unit cell. Hence the unit cell of simple cubic
structure is a primitive cell.
Each corner atom is shared by eight neighbouring unit cells so that the share of each
unit cell is only (1/8) th of an atom.
There are 8 atoms at 8 corners of unit cell.
Number of atoms = (1/8) ×8 = 1 atom/cell I.e. it is a primitive cell.
Volume of atoms per cell(v) =1x
v=
➢ Volume of unit cell (V) = a3
From fig(b), nearest neighbour distance 2r = a ,
Substitute ‘a’ value in the above equation, Therefore,
Volume of unit cell (V) = a3 = (2r) 3 = 8r3
Therefore, Packing factor =Volume occupied by atoms in unit cell/volume of unit cel
=
∏
= 6 =0.52 (or) 52%
i.e. 52% of volume of unit cell is occupied by atoms and remaining 48% is empty. So,
Simple cubic structure is a loosely packed structure. Eg.:- Polonium at
2) Body Centre Cubic Structure (BCC) :
Fig shows unit cell of B.C.C structure. It has 8 corners atoms and one extra atom at
the centre of the body. Hence; it is named as “Body centred cubic” structure.
Examples: Tungsten, Chromium, Molybdenum, etc
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All the corner atoms at the same distance from body centred atom, i.e. there are 8 atoms at the
same distance from the centre of the unit cell.
Coordination number is 8.
In a body centred crystal structure, the body centred atom touch along the diagonal of the body. In
bcc unit cell, each and every corner atom is shared by eight adjacent unit cells
1
Number of atoms = ×8+1 = 2 atom/cell
8
B.C.C is a non primitive cell
Volume of atoms per unit cell(ν) = 2x
Volume of unit cell (V) = a3
Find a:
In BCC structure, the corner atoms do not touch each other. But each corner atom touches the body
centred atom along the body diagonal as shown in figure. Therefore the two corner atoms (A and D)
situated at the opposite ends can be joined by drawing a diagonal as shown in figure.
From ∆ACD
(AD) 2 = (AC) 2 + (CD)2
= (AB) 2 + (BC 2 + (CD)2
(AD)2 = a2 + a2 +a2 = 3a2
AD = a √3 ............... (1)
From figure, The diagonal of the cube ,AD = 4r .............. (2)
From equation (1) and (2) we can write
4r = a√3
4𝑟
a =√3 ……….. (3)
therefore, Volume of unit cell (V) = a3
4𝑟
=( )3
√3
64(𝑟)3
= 3 √3
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4⨅𝑟3
2∗
3
Packing factor ,(v/V )= 64(𝑟)3
3√3
=
𝜋√3
= =0.68 0r 68%
8
i.e., 68% volume of unit cell is occupied by atoms and remaining 32% is empty. So, compare
to simple cubic structure B.C.C is closely packed structure. Eg.:-Lithium(Li) , Sodium(Na) ,
Potassium(K) , Iron(Fe) , Tungsten(W) , Chromium (Cr) etc.
3) Face Centred Cubic (FCC) Structure:-
The figure shows unit cell of F.C.C
structure.
The centre atom is surrounded by 12
points. The co-ordination number is 12.
Each corner atom is shared by 8 unit cells
and the face centred atom is shared by 2
surrounding unit cells.
16⊓(𝑟)3
Volume of atoms per unit cell(ν) = 4x =
3
The volume of unit cell =a3
To find “a”:-
Here,the two corner atoms (A and C) situated at the opposite ends of the same face can be
joined by drawing a diagonal as shown in figure.
(AC) 2 = (AB) 2 + (BC) 2
=a2+a2
(AC) 2 = 2a 2
AC = a√2 .............. (1)
But from figure, the diagonal of the cube is AC = 4r ....... (2)
From equation (1) and (2) we can write 4r = a √2
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4𝑟
a= = 2√2𝑟 ……… (3)
√2
Volume of unit cell (ν) = a3 = (2Ѵ2r) 3 =16Ѵ2r3
i.e 74% of volume of the unit cell is occupied by atoms and remaining 26% is empty. So,
compare to simple cubic and B.C.C, F.C. C has highest packing factor. So it is more closely
packed structure. Eg:- Aluminum(Al) , Copper(Cu) , Lead (Pb) , Silver(Ag), Nickel (Ni) etc.
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