1.solid State
1.solid State
Chapter 1
SOLID STATE
“Solid state of matter possesses fixed mass, volume, shape and rigidity “.
Solids are classified on the basis of arrangement of constituent particles. Due to their specific
arrangements, it shows wide range of properties and hence varied applications like as superconductors,
magnetic materials, polymers etc.
CLASSIFICATION OF SOLIDS:
Solids are classified on the basis of arrangement of their
constituent particles. If the arrangement of constituent
particles is same throughout the solid (long range order) it
is called crystalline. If the arrangement of particles does not
follow any regular pattern throughout the solid (short range
order) it is called amorphous solid.
Intext Questions:
Q.1 Classify the following solids as crystalline and amorphous.
Sodium chloride, quartz glass, quartz, rubber, polyvinyl chloride, Teflon
A.1 Crystalline solid: Sodium chloride, Quartz
Amorphous solid: Quartz glass, rubber, polyvinyl chloride, Teflon.
Q.2 why glass is considered as super cooled liquid?
A.2 Glass shows the tendency to flow at slower rate like liquid. Hence they considered as super cooled
liquid.
Q.3 why the window glass of old buildings show milky appearance with time?
A.3 Glass is an amorphous solid. Amorphous solid has the tendency to develop some crystalline character
on heating. Due to heating in day over the number of years, glass acquires some crystalline character and
show milky appearance.
Q.4 why the glass panes fixed to window or doors of old building become slightly thicker at bottom?
A.4 Glass is super cooled liquid. It has the tendency to flow down very slowly. Due to this glass pane
becomes thicker at the bottom over the time.
Q.5 Sodium chloride is a crystalline solid. It shows the same value of refractive index along all the
direction. True/False. Give reason.
A.5 False
Crystalline solid shows anisotropy in properties. That is, it shows different values for the given physical
property in different direction. All the crystalline solids show anisotropy in refractive index. Therefore
sodium chloride will show different values of refractive index on different directions.
Q.6 Crystalline solid are anisotropic in nature. What does this statement means?
A.6 Anisotropy is defined as” Difference in properties when measured along different axis or from
different directions”. Crystalline solid show different values of some of the physical properties like
electrical resistance, refractive index etc.when measured along the different directions. The anisotropy in
crystalline solid arises due to the different arrangement of particles in different directions.
Crystalline solid can be classified on the basis constituent particles and intermolecular force of attraction
in between them. Constituent particles are molecules, ions, metal kernel in sea of electrons and atoms.
Force of attraction operate in between the particles are dispersion force, dipole-dipole interaction,
hydrogen bonding, electrostatic attraction, metallic bonding and covalent bonding.
Q.2 what type of interactions hold the molecules together in a polar molecular solid.
A.2 The molecules in a solid are held together by van der Waals forces. The term van der Waals forces
include hydrogen bonding, dipole-dipole attraction and London dispersion forces. All molecules
experience London dispersion forces. In addition, polar molecules can also experience dipole-dipole
interactions. So, the interactions that holds the molecule together in polar molecular solid are London
dispersion force and dipole-dipole interactions.
Q.3 Write a feature that will distinguish a metallic solid from an ionic solid.
A.3 Metals are malleable and ductile whereas ionic solid are hard and brittle. Metallic solid has typical
metallic lustre. But ionic solid looks dull.
Q.4 Write a point of distinction between a metallic solid and an ionic solid other than metallic lustre?
A.4 Metals are malleable and ductile whereas ionic solid are hard and brittle.
Q.5 Write a distinguish feature of metallic solid.
A.5 The force of attraction in between the constituent particles is special kind of electrostatic attraction.
That is the attraction of positively charged kernel with sea of delocalized electrons.
Q.6 which group of solid is electrical conductor as
well as malleable and ductile?
A.6 Metallic solid
Q.7 why graphite is good conductor of electricity
although it is a network (covalent solid)?
A.7 The exceptional property of graphite is due to its
typical structure. In graphite, each carbon is
covalently bonded with 3 atoms in same layer. The
fourth valence electron of each atom is free to move
in between different layers.
This free electron makes the graphite a good
conductor of electricity.
In this type of arrangement spheres of both the layers are perfectly aligned horizontally and vertically.
This type of arrangement is known as AAA type closed packing of sphere in 3-dimension. The possible
smallest geometrical 3-dimensional shape would be cube. Thus this type of arrangement generate simple
cubic lattice with primitive type of unit cell.
(i) Hexagonal closed packing in three dimension:
Placing second layer over the first layer-
- Spheres in the second layer are fit in the depression of first layer.
This forms the ABCABC... type of arrangement of sphere and is known as Cubic closed packing (ccp)
or face centred cubic (fcc) structure.
Coordination number: The number of nearest neighbour touching a particle in closed packed structure is
known as the coordination number of constituent particles.
In both type of crystal lattice (hcp, ccp or fcc) the coordination number for the constituent particle is 12.
Formula of compound:
Formula of the compound is deduced by calculating number of atoms present at lattice point and number
of atoms present in voids. Generally anions are bigger and they occupy the lattice point while cations are
occupied in voids.
In a given compound, it is not necessary that all the voids are occupied by constituent particles. Some time
only fraction of voids are occupied depend on the formula of compound. Therefore it is necessary to know
the position of voids in crystal lattice.
IMPERFECTION IN SOLIDS
Although in crystalline solid there is regular arrangement of constituent particles but yet the crystals are
not perfect. There is always some king of irregularity in arrangement of constituent particles in small
crystals. These
Irregularities are known as defects in crystal. There are 2 types of defects known in crystal lattice.
Point defect
Line defect
In our syllabus only point defects are included so we will focus our study on point defects only.
POINT DEFECTS:
Impurity defect
Stoichiometric defects
Non- stoichiometric defects
Types of stoichiometric defects and Non- stoichiometric defects are mentioned in tabular form.
Stoichiometric defects Non- stoichiometric defects
Vacancy defect Metal excess defect
Interstitial defect Metal deficiency defect
Frenkel defect
Schottky defect
Impurity defect:
Impurity defect is arises due to addition of small amount of impurity in ionic solid. It actually creates
some kind of cationic vacancy in ionic solid. For example, if some SrCl2 is added in molten salt of NaCl
it takes the position of Na+ in the crystal. But charge on Sr is 2+. After removing 2 ions of Na+, Sr2+
occupy one point only. In this way it causes vacancy of 1 point.
Vacancy defect:
It arises when some of the lattice point remains unoccupied during the crystal formation.
It occurs in non-ionic compounds
It decreases the density of solid
It can be created by heating
Interstitial defect:
It arises when some of the constituent particles occupy the interstitial sites other than the lattice points.
It occurs in non-ionic compounds
It increases the density of solid
Impurity defect:
Impurity defect is arises due to addition of small amount of impurity in ionic solid. It actually creates
some kind of cationic vacancy in ionic solid. For example, if some SrCl2 is added in molten salt of NaCl
it takes the position of Na+ in the crystal. But charge on Sr is 2+. After removing 2 ions of Na+, Sr2+
occupy one point only. In this way it causes vacancy of 1 point.
Frenkel defect:
It is actually the combination of vacancy defect and interstitial defect in ionic compound. It arises when
smaller ion is dislocated from its normal site and occupies an interstitial site. It is also known as dislocation
defect.
It occurs in ionic compounds
It does not change the density of solid
Shown by ionic compound having large difference in their constituent ions.
For example: ZnS, AgBr, AgI etc.
Schottky defect:
It is actually a vacancy defect. But it causes vacancy of cation and anion both.
It occurs in ionic compounds
It decrease the density of solid
Shown by ionic compound having similar size of cation and anion.
It is actually the combination of vacancy defect and interstitial defect in ionic compound. It arises when
smaller ion is dislocated from its normal site and occupies an interstitial site. It is also known as
dislocation defect.
It occurs in ionic compounds
It does not change the density of solidShown by ionic compound having large difference in their
constituent ions.
For example: ZnS, AgBr, AgI etc.
Schottky defect:
It is actually a vacancy defect. But it causes vacancy of cation and anion both.
It occurs in ionic compounds
It decrease the density of solid
Shown by ionic compound having similar size of cation and anion
For example: NaCl, KCl, AgBr.
Important point: AgBr shows both Frenkel and schottky defect.
ELECRTICAL PROPERTIES:
Solid are classified as conductor, semi-conductor and insulator on the basis of the magnitude of
electrical conductivity.
Conductor: electrical conductivity range 104 to 107 ohm-1m-1
Semi-Conductor: electrical conductivity range 10-6 to 107 ohm-1m-1.
Insulator: electrical conductivity range 10-20 to 10-10 ohm-1m-1
CONDUCTION OF ELECTRICITY
As we know that free electrons are responsible for the conduction of electricity in metals. Electrons are
occupied in atomic orbital. The atomic orbital forms molecular orbital in metallic crystal. Molecular
orbital are very closer in energy and known as bands. To be a conductor there must be some electrons in
conduction band. But electrons are mainly occupied in valance band. On the basis of conductivity solids
are classified in 3 types: Conductor, semi-conductor, insulator.
In case of conductor there is an overlapping of valance band and conduction band.
In semi-conductor there is small gap of energy between valance band and conduction band. Some of the
electron may jump and show some activity. The metal showing this type of activity is known as intrinsic
semi-conductors. For example : Silicon and Germanium
In case of insulator there is a large energy difference between valance band and conduction band
Classification of semi-conductors:
The electrical conductivity of semi-conductors can be increased by adding some electron rich impurity or
electron deficient impurity. This is called doping.
n-type semiconductor: When the conductivity of semi-conductor is increased by adding electron rich
impurity. It generates n-type semi-conductor. For Example: when Silicon is doped with phosphorus,
phosphorus also occupies some lattice site. The covalency of Si is 4 but that of P is 5. So, one electron per
atom left unused and it delocalise from its location. This delocalise electron help in increasing conductivity
of semi-conductor.
MAGNETIC PROPERTIES:
Electrons are charged particles and it generates a magnetic field around itself. The magnetic field arises
due to the spinning of electron at its own axis and movement of atomic orbital around nucleus.
I. Paramagnetism:
Weakly attracted by magnetic fields
Alignment of magnetic dipole in the same direction of magnetic field
Loose magnetism in absence of magnetic field
They have unpaired electrons
Ex. Cu 2+, Fe 3+
II. Diamagnetism:
Weakly repelled by magnetic fields
Alignment of magnetic dipole in the opposite direction of magnetic field
They have all the electrons paired
Ex. H2O, NaCl
III. Ferromagnetism:
strongly attracted by magnetic fields
Permanently magnetised.
Ex. Fe, Co, Ni etc.
IV. Anti-Ferromagnetism:
strongly repelled by magnetic fields
Alignment of magnetic domains (group of metal ions)in the opposite direction of magnetic field..
Ex. MnO
V. Ferrimagnetisms:
Weakly attracted by magnetic fields
Alignment of magnetic domains (group of metal ions)in the parallel and anti parallel direction with
direction of magnetic field and unequal in number.
Loss magnetic moment on heating.
Ex. Fe3O4(magnetite)
Summary:
Solids have definite mass, volume and shape. This is due to the fixed position of their constituent particles
and strong intermolecular force of attraction.
Solids are classified as amorphous and crystalline.
In amorphous solids, the arrangement of constituent particles has only short
Range order. The melting point is not sharp. They are isotropic in nature. In crystalline solids there is
long range order in the arrangement of their constituent particles. The melting point is sharp. They are
anisotropic in nature.
Properties of crystalline solids depend upon the nature of interactions between their constituent particles.
On this basis, they can be divided into four categories, namely: molecular, ionic, metallic and covalent
solids.
The constituent particles in crystalline solids are arranged in a regular pattern which extends throughout
the crystal. This arrangement is often depicted in the form of a three dimensional array of points which is
called crystal lattice. Each lattice point gives the location of one particle in space. In all, fourteen different
types of lattices are possible which are called Bravais lattices. Each lattice can be generated by repeating
its small characteristic portion called unit cell
A unit cell is the smallest portion of space lattice which when repeated in different directions , generate
the entire lattice. A unit cell is characterised by its edge lengths and three angles between these edges.
Unit cells can be either primitive which have particles only at their corner positions or centred. The centred
unit cells have additional particles at their body centre (body-centred),at the centre of each face (face-
centred) or at the centre of two opposite faces (end-centred)
There are seven types of primitive unit cells. Taking centred unit cells also into account, there are fourteen
types of unit cells in all, which result in fourteen Bravais lattices
Close-packing of particles is obtained in two highly efficient lattices, hexagonal close-packed (hcp) and
cubic close-packed (ccp). The latter is also called facecentredcubic (fcc) lattice. In both of these packings
74% space is filled. Other types of packing are not close-packings and have less efficient packing of
particles. While in body-centred cubic lattice (bcc) 68% space is filled, in simple cubic lattice only 52.4
% space is filled
The remaining space is present in the form of two types of voids-octahedral voids and tetrahedral voids
Solids are not perfect in structure. There are different types of imperfections or defects in them. Point
defects and line defects are common types of defects
Point defects are of three types - stoichiometric defects, impurity defects and non-stoichiometric defects
Vacancy defects and interstitial defects are the two basic types of stoichiometric point defects. In ionic
solids, these defects are present as Frenkel and Schottky defects
Impurity defects are caused by the presence of an impurity in the crystal. In ionic solids, when the ionic
impurity has a different valence than the main compound, some vacancies are created
Nonstoichiometric defects are of metal excess defect and metal deficient defect
On the basis of electrical conductivity solids are classified as conductor, semiconductor and insulator
Sometimes calculated amounts of impurities are introduced by doping in semiconductors that change their
electrical properties. Such materials are widely used in electronics industry. They are of two types namely,
n-type semiconductor and p-type semiconductor
Solids show many types of magnetic properties like paramagnetism, diamagnetism, ferromagnetism,
antiferromagnetism and ferrimagnetism