1

Chapter
THE SOLID STATE

NCERT CRUX

 They are anisotropic in nature.

Types of Solid
 They have long range order, e.g., Diamond
Solids can be classified as crystalline or amorphous on the Amorphous Solids
basis of the nature of order present in the arrangement or their
constituent particles. In amorphous solids, the arrangement of building constituents
is not regular.
Crystalline Solids
 They have a short range order.
In crystalline solids, the arrangement of building constituents
is regular throughout the entire 3-D network.  They are isotropic in nature, e.g., glass

Classification of Crystalline Solids

Depending upon the nature of bonding, the crystalline solids have been classified into four types as given in the table below:

S. No. Types of Solid Constituent Particles Nature of Forces Example

1. Ionic Positive and negative ions. Strong electrostatic NaCl, KNO3, LiF
forces of attraction
2. Molecular Molecules Van der Waal’s forces I2, solid CO2 (dry ice), solid
CH4 , sulphur, ice.
3. Covalent Atoms Covalent bonds Diamond, Silicon
4. Metallic Positive metal ions (Kernels) and mobile Metallic bonds All metals and some alloys
electrons.

(ii) Centred Unit Cells: When a unit cell contains one or

Crystal Lattices and Unit Cells more constituent particles present at positions other
than corners it is called a centred unit cell. Centred
 Crystal Lattice: It is the 3–D arrangement of identical unit cells are of three types:
points in the space which represent how the atoms, (a) 
Body-Centred Unit Cells: Such a unit cell
ions, molecules are arranged in a crystal. contains one constituent particle (atom, molecule
or ion) at its body-centre besides the ones that are
 Unit Cell: A unit cell is the smallest portion of a space
at its corners.
lattice which, when repeated in different directions,
creates the entire lattice. (b) Face-Centred Unit Cells: Such a unit cell contains
one constituent particle present at the centre of
Unit cell is divided into two categories each face, besides the ones that are at its corners.
(i) Primitive Unit Cells :When constituent particles are (c) End-Centred Unit Cells: In such a unit cell, one
present only on the corner positions of a unit cell, it is constituent particle is present at the centre of any two
called as primitive unit cell. opposite face besides the ones present at its corners.
 2 CUET 2023-24 PW
On the basis of the axial distance and the axial angles between the edges, the primitive unit cells can be divided into seven crystal
systems.
Table: Seven Primitive Unit Cells and their Possible Variations as Centred Unit Cell
Axial Distance or Axial
Crystal System Possible Variations Example
Edge Lengths Angles
Cubic Primitive, Body-centred, a=b=c α = β = γ = 90° NaCl, Zinc blende, Cu, KCl,
Face-centred Diamond
Tetragonal Primitive, Body-centred a=b≠c α = β = γ = 90° White tin, SnO2, TiO2, CaSO4
Orthorhombic Primitive, Body-centred, a≠b≠c α = β = γ = 90° Rhombic sulphur, KNO3, BaSO4
or Rhombic Face-centred, End-centred
Hexagonal Primitive a=b≠c α = β = 90°; γ = 120° Graphite, ZnO, CdS,
Rhombohedral Primitive a=b=c α = β = γ ≠ 90° Calcite (CaCO3), HgS (cinnabar),
or Trigonal Sb
Monoclinic Primitive, End-centred a≠b≠c α = γ = 90°, β ≠ 90° Monoclinic sulphur, PbCrO4,
Na2SO4.10H2O
Triclinic Primitive a≠b≠c α ≠ β ≠ γ ≠ 90° K2Cr2O7, CuSO4.5H2O, H3BO3

 Contribution by a particle within the body of a unit

 Key Note
cell = 1
Out of the seven crystal systems, cubic crystal system is 1
 Contribution by a particle on the edge of a unit cell =
the most symmetrical (a = b = c, α = β = γ = 90°) while 4
triclinic crystal system is the most unsymmetrical system
 Key Note
(a ≠ b ≠ c, α ≠ β ≠ γ ≠ 90°).
 In a cube, there are 8 corners, 6 face centres 12
edge centres and one body centre
Number of Atoms in a Unit Cell  The atoms on the body digonals are not shared
with any other unit cell.
(i) Simple cubic  Formula of a compound is same as ratio of atoms
1 in the unit cell.
Z = 8 (corner atoms) × atom per unit cell = 1 atom
8
(ii) Body-centred cubic

Z = 8 (corner atoms) ×
1
atom per unit cell + 1
Close Packed Structures
8
(body centre atom) × 1 atom per unit cell = 1 + 1 = 2 atom (i) Close packing in one dimension
(iii) Face-centred cubic ● The coordination number in one dimension in
1
close packing is 2.
Z = 8 (corner atoms) × atom per unit cell + 6 (face
8 (ii) Close Packing in two dimensions
1 ● Square Close Packing: The coordination number
atoms) × atom per unit cell = 1 + 3 = 4 atom
2 is 4.
Contribution of n Atoms Present at Different Lattice Site ● Hexagonal Close Packing: Coordination number
is 6.
 Contribution by a particle on the corner of a unit cell
1 (iii) Close Packing in three dimensions
=
8 ● Hexagonal close packing (hcp): Coordination
1 number is 12.
 Contribution by a particle on the face of a unit cell =
2 ● Cubic close packing (ccp): Coordination number is 12.
The Solid State 3

The Different Types of Crystal Structures of Some Ionic Solids

Table: Crystal Structure of Some Cubic Ionic Solids

No. of formula per

S. No. Crystal Structure Units Brief description and Examples Co-ordination Number
Unit cell
1. Rock Salt Cl– ions form c.c.p; structure Na+ ions Na+ – 6 4
(NaCl-type) occupy all the octahedral voids. Cl– – 6
Examples: Halides of Li, Na, K and Rb,
AgCl, AgBr, NH4Cl etc.
2. CsCl - type Cl– ions at the corners of cube and forms Cs+ – 8 1
(b.c.c.) structure Cl– – 8
Cs+ ions present in the cubic void
Examples: CsCl, CsBr, etc.
3. Zinc blende (ZnS) S–2 ions form c.c.p; structure Zn+2 ions occupy Zn+2 – 4 4
alternate tetrahedral voids i.e. only half of the S–2 – 4
total number of tetrahedral voids are occupied.
Examples: ZnS, CuCl, AgI etc.
4. Fluorite structure (CaF2– Ca+2 ions (+ve ions) form c.c.p structure and Ca+2 – 8 4
type) F– ions present (-ve ions) in all the tetrahedral F– – 4
voids.
Example: CaF2, SrF2, BaF2, BaCl2 etc.
5. Antifluorite structure (Li2O– Negative ions i.e. O–2 form c.c.p. and posi- Li+ – 4 4
type) tive Li+ ions are present in all the tetrahedral O–2 – 8
voids.
Example: Na2O

Types of Voids in Crystal  Key Note

The empty spaces between close packed spheres are called
In the cubic close packing (ccp), i.e. face-centred cubic
voids or holes.
(fcc) unit cell, there are 4 atoms or ions per unit cell,
These are of different types: therefore, there are 4 octahedral voids and 8 tetrahedral
(i) Triangular void: Void between three touching spheres. voids.
 rvoid 
Radius ratio   is 0.155.
 rsphere  Ionic Solids
There are 8 triangular voids per atom in a crystal.
In ionic solids there are two type of particles that is cation
(ii) Tetrahedral void: Hole/Void between four spheres that and anion. The stability of ionic solids is described in terms
lie at the vertices of a regular tetrahedron. Radius ratio of radius ratio.
is 0.225. r radius of cation
Radius ratio
= =
(iii) Octahedral void: Void between six spheres. The R radius of anion
radius ratio is 0.414.
Greater the radius ratio, larger the size of the cation and
● There are two tetrahedral void per atom in a hence the larger is the coordination no.
crystal Table: Limiting radius ratio and structure
● There is one octahedral void per atom in a No. Radius ratio Co-ordination Shape
crystal number
(iv) Cubic void: Void formed between 8 closely packed 1. 0.0 – 0.155 2 Linear
spheres which occupy all the eight corners of a cube. 2. 0.155 – 0.225 3 Triangular Planar
3. 0.225 – 0.414 4 Tetrahedral
 r+  4. 0.414 – 0.732 6 Octahedral
Radius radio  −
 = 0.732
r  5. 0.732 – 1.0 8 Body-centred cubic
 4 CUET 2023-24 PW

Packing Efficiency Imperfection In Solids

It is the percentage of total space filled by the particles. Types of Point Defects
Packing volume occupied byatomsin unit cell (1) Stoichiometric Defects: The point defects that do
× 100 %
efficiency Total volume of the unit cell not disturb the stoichiometry of the solid are called
stoichiometric defects.
Packing efficiency in different types of structures: (a) Vacancy defect: If some of the lattice sites are
Table: Types of Unit cell and their Packing Efficiency vacant, the crystal is said to have vacancy defect.
Type of Coordination Packing Relation b/w eg. NaCl, CsCl, AgBr
Unit cell Number Efficiency a and r (b) Interstitial defect: If some constituent particles
Simple Cubic 6 52.4% 2r = a (atoms or molecules) occupy an interstitial site, the
crystal is said to have interstitial defect. Due to this
BCC 8 68 % 4r = 3a defect the density of the substance increases.
Ionic solids show these as Schottky and Frenkel
FCC 12 74 % 4r = 2a defects.
(c) Schottky defect: This defect arises if equal
number of cations and anions are missing from
Calculation Involving
a lattice. It is a common defect in ionic compounds
Unit Cell Dimensions of high coordination number where both
cations and anions are of the same size. Density
Density of Unit Cells is decreased. E.g. NaCl, KCl, CsCl, AgBr.
Let edge of a unit cell of a cubic crystal is a, d is the density of (d) Frenkel defect: This defect arises if some of the ions
the substance and M is the molar mass, then in case of cubic of the lattice occupy interstitial sites leaving lattice
crystal, Mass of unit cell = Number of atoms in unit cell × sites vacant. This defect is generally found in ionic
Mass of each atom = z × m crystals where anion size is much larger than the
Molar mass cation size e.g., AgBr, ZnS. Density is unchanged.
Mass of each atom (m) = (2) Impurity Defects: Introduction of cationic vacancy in
Avogadro number
NaCl by substitution of Na+ by Sr2+. E.g., Solid solution
M of AgCl and CdCl2.

m=
NA
(3) Non-stoichiometric Defects
z×M (i) Metal excess defect:
 Mass of unit cell =
NA (a) Metal excess defect due to anion vacancies: In
 Volume of a unit cell = a3 this defect a negative ion from the crystal lattice
can be missing from its lattice site leaving a hole
Therefore, density of the unit cell, or vacancy which is occupied by the electron
Mass of unit cell originally associated with the anion.
d=
Volume of unit cell
F-centres: The anionic sites occupied by unpaired
If molar mass and distance is given, then density is: electrons. F-centres impart colour to crystals. They
impart yellow colour to NaCl crystals, violet colour to
z×M KCl crystals and pink colour to LiCl crystals.
3
d=
× N A
a
Where z = number of atoms in unit cell, M = molar mass, (b) Metal excess defect due to interstitial cation
a = edge length, NA = 6.022 × 1023, d is in g/cm3, a in cm. In this defect an extra positive ion occupies
interstitial sites and the free electron is trapped in
the surrounding area of this interstitial cation.
 Key Note
1
Heating
ZnO → Zn 2+ + O 2 + 2e-
 Rhombohedral is similar to hexagonal close 2
The excess of Zn2+ ions move to interstitial sites
packing with 12 nearest neighbours and packing
and the electrons to neighbouring interstitial sites.
fraction of 0.74.
(ii) Metal deficiency defect: This type of defect generally
 For BCC structure of pure elements, Z = 2 but for occurs if metal shows variable valency. E.g., Fe0.93O to
BCC structure of ionic compounds like CsCl, Z = 1 Fe0.96O
The Solid State 5

five electrons present in P forms bonds with Si and Ge.

Properties of Solid One extra e– left become decocalized and is responsible
for conductivity.
Electrical Properties  p-type semiconductors: When we dope Si or Ge
 Conductors: The conductivity of solid lies between with electron deficient species like B or Al (Group 13
104 to 107 ohm–1m–1. Ex: metals. Elements), we obtain p-type semi conductor.
 Insulators: The conductivity of insulators is majorly Magnetic Properties
low with the range of 10–20 to 10–10 ohm–1m–1. Example  On the basis of magnetic properties, substances can be
plastic, woods etc. classified into five categories:
 Semiconductors: The value of conductivity lies (i) Paramagnetic
between 10–6 to 104 ohm–1m–1.
(ii) Diamagnetic
There are two types of semiconductors
(iii) Ferromagnetic
 n-type semiconductors: When we dope Si or Ge with
(iv) Anti-ferromagnetic
electron rich impurities like P (group 15 element) the
(v) Ferrimagnetic