CLASS 12 - CHEMISTRY

PREPARED BY: SONU SHARMA PREPARED BY: SONU SHARMA (8851341761)

LECTURE NOTES: 01 –B Chapter 01: Solid States

Topics Covered:
Close packing in crystals (1-D, 2-D and 3-D packing)
1.
Types of voids
2.
Location and size of voids
3.
Packing efficiency and its calculation
4.
Calculations involving unit cell dimensions
5.

Types of structures to represent a particle

Open structures – In open structures, points represent the constituent particles (atoms,
1.
ions or molecules) which are connected by lines that help to visualize the symmetry of the
crystal.
Space filling structures – In space filling structures we draw spheres wherein the centre of
2.
each sphere represents the centre of the particle.

Coordination Number – The number of nearest neighbours of a particle in a crystal is called its
coordination number.

To understand packing, we CLOSE PACKING

assume that IN CRYSTALS
constituent particles are hard spheres of identical size.

CLOSE PACKING: Close Packing means that packing of the spheres takes place such that they
occupy maximum available space with minimum empty space such that the crystal has the
maximum density.

(a) Close Packing in One Dimension

Arrange the spheres in a row touching each other. In this
arrangement, each sphere is surrounded by 2 neighbouring
spheres. So, the coordination number is 2.

(b) Close Packing in Two Dimension

When the rows of 1-D close packed spheres are placed or stacked over each other, a 2-D
close-packed structure is produced.

This can be done in two different ways:-

Method – 1
The 2nd row may be placed in contact with the 1st row such
that the spheres of the 2nd row are exactly above the
spheres of 1st row (spheres of the two rows are aligned
horizontally and vertically ). If the first row is of ‘A’ type then all other rows are also of ‘A’ type,
giving a AAA….type arrangement.

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In this arrangement, each sphere touches 4 other neighbouring

-
spheres. Thus, the two dimensional coordination number is 4.

When the centres of these 4 immediate neighbouring spheres are joined, a square is
-
formed. Hence this packing is called square close packing in two dimensions .

Method – 2
The 2nd row may be placed above the 1st row such that the spheres of 2nd row fit in the
depressions of the 1st row spheres.
Let 1st row be of ‘A’ type and 2nd of ‘B’ type. When the spheres in the 3rd row are placed
adjacent to the 2nd, its spheres are aligned with those of the 1st layer i.e. 3rd row formed is
similar to 1st row (also of ‘A’ type). Similarly, the 4th row formed will be of ‘B’ type.
Hence, this arrangement is of ABAB…type.

In this arrangement, each sphere is in contact with 6 other neighbouring spheres. Thus,
-
the two-dimensional coordination number is 6.
When the centres of these 6 immediate neighbouring spheres are joined, a regular
-
hexagon is formed. Hence this packing is called two-dimensional hexagonal close
packing.

In hcp arrangement, two different types of triangular voids are present. In one row, the
apex of the triangles is pointing upwards and in the next row it is downwards.

NOTE: Hexagonal close packing (hcp) is more efficient than square close packing because in hcp
there is less free space as more space is occupied by the spheres.

(c) Close Packing in Three Dimensions

All real structures are three-dimensional structures obtained by stacking two dimensional layers
one above the other.

Three-dimensional close packing from two dimensional square close-packed layers :

1.
Starting from 2-D square close-packed layers, the

2nd layer is placed over the 1st layer such that the
spheres of the 2nd layer are exactly above those of
the 1st layer (spheres of both the layers are perfectly
aligned both horizontally and vertically).

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 CLASS 12 - CHEMISTRY
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If we call the first layer of ‘A’ type, all the layers have

the same arrangement. Thus, the lattice formed has
AAA....type pattern. The lattice is the simple cubic
lattice, and its unit cell is the primitive cubic unit cell.

Three-dimensional close packing from two-dimensional hexagonal close packed

2.
layers: Three-dimensional close packed structure can be generated by placing layers one
over the other.

Placing second layer over the first layer

Let us take a two-dimensional hexagonal

close packed layer ‘A’ with voids marked
as ‘a’ and ‘b’.

Both the voids are triangular in shape with

vertex of voids ‘a’ pointing ‘upwards’ and
of voids ‘b’ pointing ‘downwards’.

When a 2nd layers is placed vertically


over 1st such that the spheres of the
2nd layer cover the voids ‘a’ of 1st
layer, the ‘b’ voids will be left
unoccupied.
Now, there are two types of voids in

the 2nd layer (‘c’ and ‘d’); one is
called as tetrahedral void and the
other called octahedral void.
The ‘a’ and ‘b’ voids of the 1st layer

are both triangular while only ‘c’ voids
of the 2nd layer are triangular.
The ‘d’ voids of the 2nd layer are

combinations of two triangular voids
(one each of 1st layer and 2nd layer)
A simple triangular void like ‘c’ in a crystal is surrounded by 4 spheres and is called a

tetrahedral void or a hole. A double triangular void like ‘d’ is surrounded by 6 spheres and is
called octahedral void.
These voids are called tetrahedral voids because a tetrahedron is formed when the centres of

these four spheres are joined.
In octahedral void, the triangular voids in the 2nd layer are above the triangular voids in the 1st

layer, and the triangular shapes of these do not overlap. One of them has the apex of the
triangle pointing upwards and the other downwards. Such voids are surrounded by 6 spheres
and are called octahedral voids.

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Placing third layer over the second layer

When third layer is placed over the second, there are two possibilities:

Covering Tetrahedral Voids: When the 3rd layer is placed over the 2nd layer such that
(i)
the spheres cover the tetrahedral voids ‘c’, the spheres of the 3rd layer are exactly
aligned with those of the 1st layer. Thus, the pattern of spheres is repeated in alternate
layers. This pattern is written as ABAB ....... pattern. This structure is called hexagonal
close packed (hcp) structure.
Example: Such arrangement of atoms is found in metals like magnesium and zinc.
Covering Octahedral Voids: When the 3rd layer is placed over the 2nd layer such that
(ii)
the spheres cover the octahedral voids ‘d’, the spheres of the 3rd layer are not aligned
with those of either the 1st or the 2nd layer. This arrangement is called ‘C’ type.
When 4th layer is placed, its spheres are aligned with those of the first layer
This pattern of layers is called as ABCABC ..........pattern or cubic close packing (ccp)
or face-centred cubic (fcc) structure.
Example: Metals such as copper and silver crystallise in this ccp structure.
In hcp and ccp, the coordination number is 12. (A sphere is in contact with 6 other spheres in its
own layer. It touches directly 3 spheres in the layer above and 3 spheres in the layer below. Thus
a sphere has 12 neighbours)

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Sizes of Tetrahedral and Octahedral voids

If ‘R’ is the radius of the spheres in the close packed arrangement, then

Radius (r) of tetrahedral void = 0.225 R

Radius (r)
In case of ionic compounds, of octahedral
anions voidin=the
are present 0.414 R
packing and cations occupy the voids hence:
For cations occupying the tetrahedral voids, r + = 0.225 r-
(i)
For cations occupying the octahedral voids, r + = 0.414 r-
(ii)
Tetrahedral void is much smaller than octahedral void.

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 CLASS 12 - CHEMISTRY
PREPARED BY: SONU SHARMA PREPARED BY: SONU SHARMA (8851341761)
TETRAHEDRAL VOIDS OCTAHEDRAL VOIDS

Tetrahedral void is a simple triangular void in Octahedral void is a double triangular void
a crystal surrounded by 4 spheres arranged with one triangle vertex upwards and the
tetrahedrally around it. other triangle vertex downwards and is
surrounded by 6 spheres.

Each tetrahedral void is surrounded by 4 Each octahedral void is surrounded by 6

spheres in a lattice. Hence, its coordination spheres in a lattice. Hence, its coordination
number is 4. number is 6.

As r = 0.225 R, tetrahedral void is much As r = 0.414 R, the size of octahedral void is

smaller than the size of the spheres in the much smaller than the size of the spheres in
packing. the packing, but larger than tetrahedral voids.

There are two tetrahedral voids per sphere in There is one octahedral void per sphere in the
the crystal lattice. crystal lattice.

In hcp or ccp packing, each sphere is in As octahedral void is a combination of two

contact with 3 spheres in the layer above it voids of the layers, number of octahedral
and 3 sphere below it, thus forming one voids is equal to half the number of
tetrahedral void above and one tetrahedral tetrahedral voids and hence equal to the
void below. Hence, there are 2 tetrahedral number of spheres in the packing.
voids per sphere, i.e. number of tetrahedral
voids is double the number of spheres in
packing.

Number of Voids Filled and formula of the compound

Let the number of close packed spheres be N, then:

The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
Knowing the fraction of the voids occupied, the formula of the compound can be calculated.

Locating Tetrahedral and Octahedral voids

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 CLASS 12 - CHEMISTRY
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Closed-packed structures have both tetrahedral and octahedral voids. Let us take a ccp (or
hcp) and locate these voids.
If there are ‘N’ close packed spheres, then there are ‘N’ octahedral voids and ‘2N’
tetrahedral voids.

Locating Tetrahedral Voids

o Take a unit cell of ccp or fcc lattice divide into
8 small cubes with each small cube having
atoms at alternate corners.
o Thus, each small cube has 4 atoms that on
joining to each other make a regular tetrahedron.
o Thus, there is 1 tetrahedral void in each small
cube and 8 tetrahedral voids in total.
o Each of the eight small cubes have one void
in one unit cell of ccp structure.
o ccp structure has 4 atoms per unit cell.
Thus, the number of tetrahedral voids is twice the number of atoms.

Locating Octahedral Voids

o Take a unit cell of ccp or fcc.
o The body center of the cube, C is not occupied but surrounded by 6 atoms on face centres.
o Joining the face centres creates an octahedron.
o Thus, this unit cell has 1 octahedral void at the body centre of the cube.
o Also, there is 1 octahedral void at the centre of each of the 12 edges.
o It is surrounded by 6 atoms, 4 belonging to the same unit cell (2 on corners and 2 on face centres) and
2 belonging to the two adjacent unit cells.
o Each edge of the cube and octahedral void are shared between four adjacent unit cells.
o Only ¼ of each void belongs to a particular unit cell

Thus, In Cubic-close packed structure:

Octahedral void at the body-center of the cube = 1
1
12 octahedral voids located at each edge and shared between four unit cells =12 x =3
4
Therefore, Total number of octahedral voids = 4

In ccp structure, each unit cell has 4 atoms. Thus, the number of octahedral voids is equal to this number.

Relationship between edge length of unit cell (a) and radius of sphere (r)

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 CLASS 12 - CHEMISTRY
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Relationship between nearest Relationship between Packing
UNIT CELL neighbour distance (d) and edge edge length ‘a’ and atomic Efficiency
(a) of a unit cell radius ‘r’

Simple cubic d=a a 52.4%

r=
lattice 2

BCC structure
d=
√3 a r=
√3 a 68%
2 4
FCC structure a a 74%
d= r=
√2 2 √2

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For Ionic Compounds

Z = No. of formula units in one unit cell e.g. for NaCl and ZnS (Z=4), for CsCl (Z=1)
Remember: For BCC structure of an element (like alkali metals), Z = 2

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 CLASS 12 - CHEMISTRY
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For BCC structure of ionic compounds (like CsCl), Z = 1

INTEXT QUESTIONS…………..PAGE NO. 23 and 24

1.14 What is the two dimensional coordination number of a molecule in square close-
packed layer?
In two-dimensional square close-packed layer, each sphere (atom) is in contact with 4 of its
neighbouring spheres (atoms).
Hence, the two dimensional coordination number is 4.

1.15 A compound forms hexagonal close-packed structure. What is the total number of
voids in 0.5 mol of it? How many of these are tetrahedral voids?

Number of atoms in 0.5 mol close packing = 0.5 × 6.022 × 1023 = 3.011 × 1023

Number of octahedral voids = Number of atoms in the packing = 3.011 × 10 23

Number of tetrahedral voids = 2 × Number of atoms in the packing

= 2 × 3.011 × 10 23  = 6.022 × 1023

Total number of voids = Octahedral voids + Tetrahedral voids

= 3.011 × 10 23 + 6.022 × 1023
=
9.033 × 1023

1.16 A compound is formed by two elements M and N. The element N forms ccp and atoms of
M occupy 1 /3rd of tetrahedral voids. What is the formula of the compound?

Suppose no. of atoms of element ‘N’ present in ccp = ‘A’

Number of tetrahedral voids = ‘2A’

1
Since rd of tetrahedral voids are occupied by atoms of element M.
3
1 2A
So, number of atoms of element ‘M’ =   × 2A =
3 3

2A
Ratio of M and N = M : N = : A  = 2 : 3
3
Formula of the compound = M2N3

1.17 Which of the following lattices has the highest packing efficiency (i) simple cubic (ii)
body- centred cubic and (iii) hexagonal close-packed lattice?
Packing efficiencies are: In Simple cubic – 52.4 %,
Body-centered cubic – 68%
Hexagonal close-packed – 74%
Hence hcp lattice has the highest packing efficiency.

1.18 An element with molar mass 2.7 × 10-2 kg mol-1 forms a cubic unit cell with edge length
405 pm. If its density is 2.7 × 103 kg m-3, what is the nature of the cubic unit cell?

Given: Molar mass of element = M = 2.7 ×10−2 kg mol−1

Edge length = ‘a’ = 405 pm = 405×10−12 m = 4.05×10−10 m
Density = ‘d’ = 2.7×10 3 kg m−3
Avogadro number = N A = 6.022×10 23 mol−1

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Z ×M
Using the formula d=
a3× N A

Number of atoms of the element present per unit cell = 4.

Hence, the cubic unit cell must be face-centred or cubic dose packed (
ccp).

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