TYPES OF VOIDS FOUND IN CLOSE PACKING

1. Tetrahedral void (3-Dimensional 4 co-ordinate) :

The tetrahedral void is formed whenever a sphere is placed on top of the triangular arrangement as in case of the triangular void.

r = 0.225 R

Location of tetrahedral voids in FCC unit cell :

The FCC unit cell has eight tetrahedral voids per unit cell. Just below every cornerof the unit cell, there is one. As there are eight corners, there are eight tetrahedral voids.

The spheres 1, 2, 3, 4 form a tetrahedral void.

2. Octahedral void (3-Dimensional 6 coordinate void) The octahedral void is formed whenever two spheres are placed, one on top and the other below a square arrangement of spheres

r = 0.414 R

Location of octahedral voids in a FCC unit cell :

In a FCC unit cell, there are four octahedral voids. They are present at all the edge centres and at the body centre. The contribution of the edge centre void per unit cell is     .

Hence, total number of octahedral voids = +  (1)  = 4

edge centres           body centre

Note : Let the no. of close packed spheres be N then the no. of octahedral void gemetrated = N and the number of tetrahedral void generated = 2N

3. Cubical void (3-Dimensional 8-coordinate void)

The cubical void is generally not found in closed packed structures, but is generated as a result of distortions arising from the occupancy of voids by larger particles.

Along body diagonal

r = 0.732 R

IONIC SOLIDS :

Ionic solids are characterised by the presence of atleast two types of particles,viz: the cation and the anion,even the simplest of ionic solids contains one cation and one anion.

The Cations are generally found to be of smaller size, and the anions of larger sizes. The anions thus form the lattice by occupying the lattice positions and the cations are found inside the voids in such structures.

The types of void occupied by the cation would depend upon the the ratio of its radius to that of the anion, popularly termed as the radius ratio. Hence, radius ratio = r+ / r

Examples of ionic crystals :

(a) Rock Salt (NaCl) Coordination number (6 : 6) NaCl crystallizes in the face centred cubic structure. The chloride ions are present at all the lattice position and the sodium ions occupy all the octahedral voids.

Every sodium is in contact with four chloride ions, and every chloride is in contact with four sodium ions

(b) CsCl  C.No. (8 : 8)

The cesium ion is at the body centre and the chloride ions are at the corners.

(c) Zinc Blend (ZnS) C.No. (4 : 4)

(d) Fluorite structure (CaF2) C.No. (8 : 4)