4. No.

of atom per Unit Cell, Coordination Number, Packing fraction

XRD

Solid state-4
 Characteristics of unit cell:
1. Number of atoms per unit cell
2. Coordination number
3. Atomic radius
4. Atomic Packing factor or Packing Density

• Coordination number: The number of equidistant nearest neighbouring atoms surrounding the
particular atom considered.

• Atomic Radius (r): It is defined as half the distance between the nearest neighbouring atoms in a
crystal.

• Atomic Packing factor or Packing Density: It is the ratio of the volume occupied by the atoms in a
unit cell (v) to the volume of the unit cell (V). It is also called packing fraction.
 Characteristics of unit cell:

1. Simple cubic structure - SCC

2. Body centered cubic structure- BCC
3. Face centered cubic structure- FCC
4. Hexagonal closed packed structure- HCC
 Packing of Crystals – Coordination Number
• When crystal formation takes place, the constituent particles (atoms, ions or molecules) get closely packed
together in such a way that they occupy the maximum available space. This type of packing is called close
packing.
• To understand packing of the constituent particles of crystals, it is assumed that all the spheres are of equal
size. The packing of spheres takes place as follows:
• (i) Simple cubic packing: It is the simplest possible arrangement of atoms. The atoms in the first layer are placed
side by side. The atoms of the next layer are placed directly above the atoms of the first layer. Each atom is in
direct contact with six atoms in its close vicinity (four in its plane, one atom in the layer above it and one in
the layer below it.
• The number of atoms (spheres) touching a given sphere is called its coordination number.
• Thus, the coordination number of each atom in simple cubic or primitive cubic packing is six. This
arrangement of atoms is not very compact.
• Ex: Among metals, only polonium is reported to have this type of crystal lattice.
 Packing of Crystals – Coordination Number
• (ii) Body centred cubic (BCC): In this type of packing, the spheres in the first layer are arranged like
the spheres in simple cubic packing. However, the spheres of the second layer are not placed
directly above the spheres of the first layer; rather they fit into the holes between adjacent spheres
of the first layer. Similarly, the spheres of the third layer fit into the holes between adjacent spheres of
the second layer. The third layer is exactly similar to the first layer.

• Each atom touches four atoms in the layer above it and four in the layer below its plane.

• Thus, the coordination number of a BCC is eight.

• Ex: Metals like Li, Na and K crystallise into a BCC arrangement.

• (iii) Hexagonal closed packing (HCP): In this type of packing, the atoms in the first layer have a hexagonal arrangement in

which each sphere has six spheres in its immediate vicinity (Fig. a).

• There are two types of voids in the first layer. They are marked as ‘a’ and ‘b’ (Fig. b). All the voids are equivalent but the

atoms of the second layer are placed either on the voids marked ‘a’ or on the voids marked ‘b’ (Fig. c).

• It may be noted that since the atoms are much closer to each other, it is not possible to place atoms on both types of voids.

When the third layer of atoms is to be placed, they may be placed on the voids on the second layer (marked ‘c’).

• In this arrangement, the spheres of the third layer lie directly above those of the first layer. In other words, the third layer

becomes exactly identical to the first layer.

• This type of packing is termed as ABABA arrangement. It can also be called the hexagonal closed packing abbreviated as

HCP (Fig.) The coordination number in both HCP packing is 12. (six atoms in its own layer, three atoms in the layer

above it and three in the layer below it).

• Ex: Metals having hexagonal closed packing structures are Ba, Co, Mg and Zn
• (iv) Cubic closed packing (CCP or FCC) An alternative way to pack the atoms of the third layer is to place them over
voids marked ‘a’ (unoccupied voids of the first layer). This gives rise to a new layer labelled as ‘c’. In this type of
arrangement, the atoms of the fourth layer will correspond to those in the first layer (Fig.).

• This gives the ABCABCA type of arrangement.

• It is also known as cubic closed packing (CCP) or face centred packing (FCC) arrangement.

• The coordination number in both FCC packing is 12 (six atoms in its own layer, three atoms in the layer above it and three in
the layer below it).

• Ex: Metals like Ag, Au, Ca, Co, Cu and Ni have CCP structures.
Packing Efficiency and Atomic Radius
X Ray Diffraction and Bragg’s Law
 X Ray Diffraction
The atomic planes of a crystal cause an incident beam of X rays to interfere with one another as they leave the
crystal. The phenomenon is called X-ray diffraction

The arrangement of particles in crystalline solids is determined indirectly by X ray Diffraction- single diffraction
spots .
 Powder X- Ray
Diffraction:
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a
crystalline material and can provide information on unit cell dimensions.

In other methods a single crystal is required whose size is much larger than microscopic dimensions. However,
in the powder method as little as 1 mg of the material is sufficient for the study.

For every set of crystal planes , one or more crystals will be in the correct orientation to give the correct Bragg
angle to satisfy Braggs equation. Each diffraction line is made up of a large number of small spots, each from
a separate crystal. Each spot is so small as to give the appearance of a continuous line. Every crystal plane is thus
capable of diffraction.- generating only single diffraction spots

In the year 1913, Sir W H Bragg and his son Sir W L Bragg studied the phenomenon of diffraction of X-rays by
crystals, for which, in 1915, they were awarded the Nobel prize in physics.
 The powdered sample generates the concentric cones of diffracted X-rays. This is called powder pattern.
Hence, instead of the sample generating only single diffraction spots, it generates cones of diffracted X-rays.
The powder diffracts the x-rays in accordance with Bragg’s law to produce cones of diffracted beams. These
cones intersect a strip of photographic film located in the cylindrical camera to produce a characteristic set of
arcs on the film. When the film is removed from the camera, flattened and processed, it shows the diffraction
lines and the holes for the incident and transmitted beams
 Powder XRD: Circular Diffraction Pattern
 Single Crystal Diffraction Pattern

Each diffraction line is made up of a large number The powdered sample generates the concentric cones of
of small spots, each from a separate crystal. diffracted X-rays - arcs on the film

Each spot is so small as to give the appearance of a

continuous line
Braggs Law: X-Ray Study of Crystals
 Braggs Law :
 In 1913 Bragg found that Laue photographs are more easily interpreted by treating the crystals as a reflecting
grating rather than a diffraction grating. In which the crystal spacings can be determined by use of X
rays .Braggs used to explain the interference pattern of x rays scattered by crystals.

 Diffraction occurs only when Bragg’s Law is satisfied condition for constructive interference (X-rays 1 & 2) from planes with
spacing “d”.
• They gave Bragg’s law, which states that ‘when X-ray is incident on a crystal, it is diffracted from the atoms in the crystal
planes and obeys the laws of reflection. If the angle of incidence is θ, then the angle of reflection will also be the same, that
is, θ. Constructive interference will occur if the path difference between the two rays reflected from successive planes is an
integral multiple of their wavelengths.
• Bragg’s equation can be derived as given below:
Let two parallel beams of X-rays P and Q fall on a crystal plane at an angle θ (Fig. 11.18). They will be reflected by the same
angle. Let the wavelength of these X-rays be λ. The two successive planes of the crystal are separated by a distance d. The X-
ray beam P is reflected from the first plane and the beam Q enters the crystal and is reflected from the second plane. The ray Q
reflected from the second plane travels an extra distance equal to CB + BD.
• Now according to Bragg’s law, constructive interference will occur if this extra distance is equal to an integral multiple of
the wavelength, that is
Defects in crystals
 Imperfection in Solids
• An ideal crystals exist only at absolute zero (0 K) temperature. At absolute zero, the crystal is highly ordered but above 0 K,
they deviate from the perfectly ordered arrangement. The term defect or disorder or imperfection is used to denote
departure from the perfectly ordered arrangement of the constituent particles. Imperfection results in change of properties.
• Generally, there are two types of imperfections – electronic imperfections and atomic imperfections.
• 1. Electronic imperfections:
These are defects in ionic crystals due to electrons. In an ideal crystal at 0 K, the electrons occupy the fully occupied lowest
energy states but at a temperature above 0 K, some of these electrons may occupy higher energy states. Electrons may be
released from covalent bonds and they may become free to move. The bonds from which the electrons are removed become
electron deficient and these are termed as holes. Free electrons and holes in the crystals are called electronic imperfections.
The presence of free electrons and holes increases the conductivity of the crystal.
• For example, in silicon and germanium, the concentration of electrons and holes will be equal. However, holes and electrons
can be preferentially produced by adding trivalent impurity (e.g., B, Al, Ga) or pentavalent impurity (e.g., P, As) in Si or Ge
crystal, which makes them semiconductors
• 2. Atomic imperfections
Atomic imperfections are also termed as point defects and arise due to irregularity in the arrangement of atoms or ions in the
crystal.
Point defects may arise when either
• some constituent particles are missing from their position or
• the constituent particles shift from their positions and occupy interstitial spaces.
Problem
Problem
 Problem
• Xenon crystallises into a face centred cubic lattice. The edge of the unit cell is 620 pm. Find
the distance with the nearest neighbour and radius of the xenon atom.
Edge length a = 620 pm
Problem
Problem