Chapter-1

The Solid State

Solid - Solid is a state of matter in which the constituting particles are arranged very closely. The
constituent particles can be atoms, molecules or ions.
Properties of solids
1. They have definite mass, volume and shape.
2. Intermolecular distances are short and hence the intermolecular forces are strong.
3. Their constituent particles have fixed positions and can only oscillate about their mean
positions.
4. They are incompressible and rigid.
Classification of solids based on the arrangement of constituent particles -
1. Crystalline solids - The arrangement of constituent particles is a regular orderly arrangement.
Example - iron, copper, diamond, graphite
2. Amorphous solids - The arrangement of constituent particles is an irregular arrangement.
Example - Glass, plastics, rubber
Properties of crystalline solids
1. They have a definite characteristic geometrical shape.
2. They have a long-range order.
3. They have a sharp melting point.
4. They are anisotropic in nature i.e. their physical properties show different values when
measured along different directions in the same crystal.
5. When cut with a sharp edged tool, they split into two pieces and the newly generated surfaces
are plain and smooth.
6. They have a definite and characteristic heat of fusion.
7. They are called true solids.
Polymorphic forms or polymorphs - The different crystalline forms of a substance are known as
polymorphic forms or polymorphs. For example - graphite and diamond.
Characteristics of amorphous solids -
1. They have an irregular shape.
2. They have a short-range order.
3. They gradually soften over a range of temperature.
4. They are isotropic in nature i.e. their physical properties are the same in all directions.
5. When cut with a sharp edged tool, they cut into two pieces with irregular surfaces.


6. They do not have definite heat of fusion.
7. They are called pseudo solids or super cooled liquids. This is because they have a tendency to
flow, though very slowly.
Crystal lattice - A regular ordered arrangement of constituent particles in three dimensions is called
crystal lattice.
Lattice points or lattice sites - The fixed positions on which the constituent particles are present are
called lattice points or lattice sites. A group of lattice points which when repeated over and over again in
3 dimensions give the complete crystal lattice.
Unit cell - The unit cell is defined as the smallest repeating unit in space lattice which when repeated
over and over again generates the complete crystal lattice. The crystal can consist of an infinite number
of unit cells.
Parameters that characterize a unit cell -
1. Dimensions of the unit cell along the three edges, a, b and c - These edges may or may not be
mutually perpendicular.
2. Inclination of the edges to each other: This is denoted by the angle between the edges , , and
respectively. is the angle between the edges b and c, is the angle between the edges a and
c, and is the angle between a and b.
Seven crystal systems -
1. Cubic: = = = 90 , a = b = c
2. Tetragonal: = = = 90 ; a = b c
3. Orthorhombic: = = = 90; a b c
4. Monoclinic: = = 90, 90; a b c
5. Hexagonal: = = 90, =120; a = b c
6. Rhombohedral or trigonal: == 90; a = b = c
7. Triclinic: 90; a b c
Types of unit cells -
1. Primitive or simple unit cells have constituent particles only at its corners.
2. Centred unit cells are those unit cells in which one or more constituent particles are present at
positions in addition to those present at the corners.
The centred unit cells are of three types -
1. Face centred unit cell - A face centred unit cell consists of one constituent particle present at
the centre of each face in addition to those present at the corners.
2. Body centred unit cell - A body centred unit cell consists of a one constituent particle is present
at its body centre in addition to those present at the corners.


3. End centred unit cell - An end centred unit cells consists of one constituent particle present at
the centre of any two opposite faces in addition to those present at the corners.
Number of particles at different lattice positions -
1. Corner - If an atom is present at any one corner, it is shared by eight unit cells. Therefore, only
one eighth of an atom actually belongs to the unit cell.
2. Face centre - If an atom is present at the centre of the face, it is shared by two unit cells.
Therefore, only half of the atom actually belongs to the unit cell.
3. Body centre - If an atom is present at the body centre, it is not shared by any other unit cell.
Therefore, that one atom completely belongs to the same unit cell.
4. End centre - If an atom is present at the edge centre, it is shared by four unit cells. Therefore,
only one fourth of an atom belongs to the unit cell.
Number of atoms in different unit cells -
1. Primitive unit cell - 1 atom
2. Face centred unit cell - 4 atoms
3. Body centred unit cell - 2 atoms
Coordination number - It is the number of nearest neighbours of a particle.
Close packed structures -
1) Close packing in one dimension - Each sphere is in contact with two of its neighbours. Coordination
number is two.
2) Close packing in two dimensions - It is generated by stacking the rows of close packed spheres in
two ways -
a) Square close packing - When the spheres of the second row are placed exactly above those of
the first row. This way the spheres are aligned horizontally as well as vertically. The arrangement
is AAA type. Coordination number is 4.
b) Hexagonal close packing - When the spheres of the second row are placed above the first one in
a staggered manner in such a way that its spheres fit in the depression of the first row. The
arrangement is ABAB type. Coordination number is 6.
3) Close packing in three dimensions - They can be obtained by stacking the two-dimensional layers
one above the other. It can be obtained in two ways -
a) Three-dimensional close packing from two-dimensional square close packed layers - Here, The
spheres of the upper layer are placed exactly over the first layer such the spheres of the layers
are perfectly aligned horizontally and vertically. It has an AAAA type pattern. The lattice is
simple cubic lattice.
b) Three dimensional close packing from two dimensional hexagonal close packed layers - There
are two steps involved as:
i) Placing the second layer over the first layer: if a two-dimensional layer is considered as A,
the second layer which is placed above the first layer in such a way that the spheres of the


second layer (considered as B) are placed in the depressions of the first layer. This gives rise
to two types of voids: tetrahedral voids and octahedral voids.
ii) Placing the third layer over the third layer: There are two possibilities:
(1) Covering the tetrahedral voids - Here, tetrahedral voids of the second layer may be
covered by the spheres of the third layer. It gives rise to ABABAB type pattern. The
three dimensional structure is called hexagonal close packed structure. Coordination
number is 12. Example - Mg, Zn
(2) Covering the octahedral voids - Here, octahedral voids of the second layer may be
covered by the spheres of the third layer. It gives rise to ABCABCABC type pattern. The
three dimensional structure is called cubic close packed structure or face centred cubic
structure. Coordination number is 12. Example - Cu, Ag
Types of voids -
1) Tetrahedral voids - This type of void is formed at the centre when four spheres are joined in the
form of a tetrahedron.
2) Octahedral void - This type of void is surrounded by six spheres.
In hcp or ccp arrangement, octahedral and tetrahedral voids are present. The number of octahedral
voids present in a lattice is equal to the number of closely packed particles. The number of tetrahedral
voids is twice the number of octahedral voids.
Example - If the number of close packed particles = n
Number of particles present in octahedral voids = n
Number of particles present in tetrahedral voids = 2n
Packing efficiency- is the percentage of total space occupied by constituent particles (atoms, molecules
or ions)
Volumeoccupiedbyspheres
Packing efficiency x100%
Totalvolumeofunitcell
1) Packing efficiency for face centred unit cell =74%
2) Packing efficiency for body centred cubic unit cell =68%
3) Packing efficiency for simple cubic unit cell =52.4%
Radius ratio in an octahedral void - For an atom to occupy an octahedral void, its radius must be 0.414
times the radius of the sphere.
r/R=0.414


Radius ratio for tetrahedral void - For an atom to occupy a tetrahedral void, its radius must be 0.225
times the radius of the sphere.
r/R=0.225
Density of a unit cell is same as the density of the substance.
Relationship between radius of constituent particle (r) and edge length(a) -
1. Simple cubic unit cell: a= 2r
2. Face centred unit cell: a =
3. Body centred unit cell: a=

Number of atoms in a unit cell (z) -
1. Simple cubic unit cell: z = 1
2. Face centred unit cell: z = 4
3. Body centred unit cell: z = 2
Density of unit cell =

Crystal defects - are irregularities in the arrangement of constituent particles.Defects are of two types:
1. Point defects - Point defects are the irregularities or deviations from ideal arrangement around a
point or an atom in a crystalline substance.
2. Line defects - Line defects are the irregularities or deviations from ideal arrangement in entire
rows of lattice points.
Point defects are of three types:
1. Stoichiometric, intrinsic, or thermodynamic defects: These point defects do not disturb the
stoichiometry of the solid.
2. Non stoichiometric defects: These point defects disturb the stoichiometry of the solid.
3. Impurity defects: These are the defects in ionic solids due to the presence of impurities present
in them.
Stoichiometric defects for non- ionic solids are of two types:
1. Vacancy defect - A crystal is said to have vacancy defect when some of the lattice sites are
vacant.This results in decrease in density of the substance.
2. Interstitial defect - A crystal is said to have interstitial defect when some constituent particles
(atoms or molecules) occupy an interstitial site.This results in increase in density of the
substance.
Stoichiometric defects for ionic solids are of two types:


Schottky defect - In this defect equal number of cations and anions are missing. For example -NaCl, KCl,
CsCl and AgBr.
Frenkel or dislocation defect - In this defect, the smaller ion (usually cation) is dislocated from its
normal site to an interstitial site.For example -ZnS, AgCl, AgBr and AgI.
Non-stoichiometric defects are of two types:
1. Metal excess This type of defect is due to excess of metal cations. These may be due to:
a. Anionic vacancies: A compound may have an extra metalion if the negative ion is absent
from its lattice site. This empty lattice site is called a hole. To maintain electrical
neutrality this site is occupied by an electron. The hole occupied by an electron is called
f-centre or Farbenzentercentre. F-centre is responsible for the colour of the compound.
b. Presence of extra cations: A compound is said to have extra cations if a cation is present
in the interstitial site. An electron is present in the interstitial site to maintain the
electrical neutrality.
2. Metal deficiency - This defect arises because of absence of metal ions from its lattice sites. The
electrical neutrality is maintained by an adjacent ion having a higher positive charge.
Solids can also be classified into three types based on their electrical conductivities:
1. Conductors-The solids with conductivities ranging between 10
4
to 10
7
ohm
1
m
1
are called
conductors.
2. Insulators - These are the solids with very low conductivities ranging between 10
20
to 10
10

ohm
1
m
1
.
3. Semi-conductors - These are the solids with conductivities in the intermediate range from 10
6

to 10
4
ohm
1
m
1
.
Band theory A metal is characterized by a band structure. The highest filled band is called valence
band and the lowest unoccupied band is called conduction band. The gap between the two bands is
called forbidden band.
1. In case of conductors, the valence band and conduction band overlap
2. In case of insulators, the forbidden gap is very large and the electrons are unable to excite to the
conduction band.
3. In case of semiconductors, forbidden gap is small. Therefore, some electrons may jump to
conduction band and show some conductivity. Electrical conductivity of semiconductors
increases with rise in temperature, since more electrons can jump to the conduction band.
Types of semiconductors:
1. Intrinsic: The forbidden gap is small in these semiconductors. Only some electrons may jump to
conduction band and show some conductivity. They have very low electrical conductivity.
Example: Silicon, germanium


2. Extrinsic: When an appropriate impurity is added to an intrinsic semiconductor. Their electrical
conductivity is high.
Doping - The process of adding an appropriate amount of suitable impurity to increase the conductivity
of semiconductors.
Types of extrinsic semiconductors:
n-type semiconductors - They are formed when silicon is doped with electron rich impurity like group 15
elements.The increase in conductivity is due to the negatively charged electrons.
ptype semiconductors - They are formed when silicon is doped with electron deficient impurity like
group 13 elements.The increase in conductivity is due to the positively charged holes.
Diode: It is a combination of n-type and p-type semiconductors and is used as a rectifier.
Transistors: They are made by sandwiching a layer of one type of semiconductor between two layers of
the other type of semiconductor. npn and pnp type of transistors are used to detect or amplify radio or
audio signals.
12- 16 compounds These compounds are formed by the combination of group 12 and group 16
compounds. They possess an average valency of 4. Example: ZnS, CdS, CdSe and HgTe
13- 15 compounds These compounds are formed by the combination of group 13 and group 15
compounds. They possess an average valency of 4. Example: InSb, AlP and GaAs
Every substance has some magnetic properties associated with it. The origin of these properties lies in
the electrons. Each electron in an atom behaves like a tiny magnet. Its magnetic moment originates
from two types of motions (i) its orbital motion around the nucleus and (ii) its spin around its own axis.
Based on their magnetic properties, substances can be classified into five categories:
1. Paramagnetic: These substancesare weakly attracted by the magnetic field. It is due to presence
of one or more unpaired electrons.
2. Diamagnetic: Diamagnetic substances are weakly repelled by a magnetic field. Those substances
in which all the electrons are paired show diamagnetism and there are no unpaired electrons.
3. Ferromagnetic: These substancesare attracted very strongly by a magnetic field.
4. Antiferromagnetic: They have equal number of parallel and anti-parallel magnetic dipoles
resulting in a zero net dipole moment.
5. Ferrimagnetic: They have unequal number of parallel and anti-parallel magnetic dipoles
resulting in a net dipole moment.
Dielectric properties of Solids - Depending upon the alignment of electric dipole the solids have
following character.


Piezo Electricity -A di-electric crystal that has resultant dipole movement and can produce electricity
when external pressure is applied such as crystal is called piezo electric crystal and the property is
termed as piero electricity.For example - Lead Zirconate (

), Ammonium, di- hydrogen phosphate

(

)
Pyro electricity (heat pyro) -Certain crystals on heating produce electric current this phenomena is
called pyro electricity.
Ferro Electricity (Sam to ferromagnetic substance) -In such crystals dipole are permanently polarized
even in the absence of electric field. For example - Sodium Potassium Tartrate (Rochelles Salt)

Problems
1. Calculate the no. of atoms, in a cubic-based unit cell having 1atom on each corner and 2 atoms
of on each body diagonal.
2. A metal of atomic mass 50 has BCC structure density= 5.96g/cc. Calculate the volume.