POORNIMA INSTITUTE

EXCELLENCE IN QUALITY EDUCATION

SCIENCE AND COMMERCE ( VII-XII, NTSE, KVPY )

B CHEMISTRY
​

Booklet

TOPIC​ -​ SOLID STATE

​(Chemistry CHAPTER- 01)

CLASS-XII

DIRECTOR: ​ANKIT SAINI - 779099503

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IMPERFECTIONS OR DEFECTS IN SOLIDS
The discovery of imperfections in an otherwise ideally perfect crystal is one of the most fascinating
aspects of solid state science. An ideally perfect crystal is one which has the same unit cell and contains
the same lattice points throughout the crystal.
However set ideal questions exist only at absolute 8k temperature.at any temperature above zero kelvin
the crystals have some deviation from complete order arrangement.
The term imperfection or defect is generally used to describe any deviation of the ideally perfect crystal
from the periodic arrangement of its constituents.

ATOMIC IMPERFECTIONS / POINT DEFECTS

If the deviation occurs because of missing atoms, displaced atoms or extra atoms, the imperfection is
named as a point defect.

Such defects can be the result of imperfect packing during the original crystallisation or they may arise
from thermal vibrations of atoms at elevated temperatures because with increase in thermal energy there
is increased probability of individual atoms jumping out of their positions of lowest energy.

Type of point defects –> point defects in a crystal may be classified into three types

● Stoichiometric defects
● Non – stoichiometric defects
● Impurity defects

STOICHIOMETRIC DEFECTS
The compounds in which the number of cation and anions are exactly in the same ratio as represented
by their chemical formula are called stoichiometric compounds. The defects that do not disturb the ratio
of cations and anions are called stoichiometric defect.

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These are of four types

● Vacancy Defect
● Interstitial Defect
● Schottky Defect
● Frenkel Defect

Vacancy Defect
● When some of the lattice sites are vacant, the crystal is said to have vacancy defect .
● This results in a decrease in density of the substance.
● This defect can also develop when a substance is heated.

Interstitial Defect
● When some constituent particles (atoms or molecules) occupy an interstitial site, the crystal is
said to have interstitial defect
● This defect increases the density of the substance.

Schottky Defect
If in an ionic crystal of the type A+ B-, equal number of cations and anions are missing from their
lattice. It is called Schottky defect.
This type of defect is shown by highly ionic compounds which have

● High Co – ordination number and

● Small difference in the sizes of cations and anions

A few examples of ionic compounds exhibiting Schottky defect are NaCl, KCl, KBr and CsCl.

Consequences of Schottky Defect

● As the number of ions decreases as a result of this defect, the mass decreases whereas the
volume remains the same. Hence density of the solid decreases
● The crystal begins to conduct electricity to a small extent by ionic mechanism
● The presence of too many voids lowers lattice energy and the stability of the crystal

Frenkel Defect
If an ion is missing from its correct lattice sites (causing a vacancy or a hole) and occupies an
interstitial site, electrical neutrality as well as the stoichiometry of the compounds are maintained.
This type of defect is called Frenkel defect. Since cations are usually smaller it is more common to
find the cations occupying interstitial sites.

● This type of defect is present in ionic compounds which have

● Low coordination number
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Larger difference in size of cation and anions

Compounds having highly polarising cation and easily polarisable anion. A few examples of ionic
compounds exhibiting this defect are AgCl, AgBr, AgI, ZnS, etc.

Consequences of Frenkel defect

● As no ions are missing from the crystal lattice as a whole, therefore the density of the solid
remains the same
● The closeness of like charges tends to increase the dielectric constant of the crystal
● The crystal conducts electricity to a small extent by ionic mechanism

NON – STOICHIOMETRIC DEFECTS

If as a result of imperfection, the ratio of number of cation to anion becomes different from that
indicated by the ideal chemical formula, the defects are called non – stoichiometric defects.
These defects arise either due to excess of metal atoms or nonmetal atom or presence of impurities /
foreign particles.
They are of two types:-

1. Metal excess defects:-

I)​ ANIONIC VACANCIES
A negative ion may be missing from its lattice site, leaving a hole which is occupied by an
electron, thereby maintain the electrical neutrality.
The interstitial sites containing the electron thus trapped in the anion vacancies are called the F –
centers. They are responsible for imparting colour to the crystals.
Example:- When NaCl is heated in an atmosphere of Na vapours. The excess of Na atoms deposition
the surface of NaCl crystal Cl- ions then diffuse to the surface where the combine with Na+ ions which
becomes due to losing electrons.
These electrons loses by Na atom are diffuse back into the crystal and occupy the vacant site created by
Cl- ions and imparts Yellow colour to NaCl crystal

II. By Presence Of Extra Cation In Interstitial Sites:-

• Metal excess may also be caused by an extra cation occupying the interstitial site. For example when
ZnO is heated it loses oxygen and turns yellow due to following

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ZnO → Zn+2 + (1/2)O2 + 2e-
The excess interstitial sites and the electrons in neighbouring interstitial sites.

Metal Deficiency Defect​:-

This defect is due to less number of cations than anions.These are of two types-

A) Cation Vacancies –
In this defect cations may be missing from their lattice sites.The extra negative charge may be balanced
by some metal ion having two positive charges instead of one . Generally transition metals show this
defect.
For example it is difficult to prepare ferrous oxide with ideal composition because ferum exists as both
Fe+2 and Fe+3 ions thus we obtain Fe0.95O or FexO with x = 0.93 to 0.96

B) Extra Anions Occupying Interstitial Sites-

In this defect , the extra anions may be occupying interstitial sites.The extra negative charge is balanced
by some metal ion having extra charges.
Ex. ZnO

impurity Defects:-
These defects are arises when foreign atoms are present at the lattice site in place of the host atom.
Or it is present at the vacant interstitial site example n – type semiconductor, p – type semiconductor . If
molten NaCl containing a little amount of SrCl​ 2​ is slowed to crystallize, some of the sides of sodium
positive ions(Na​+​) are occupied by Sr​2+ ​ions . for each Sr​2+​iron introduced to sodium ions are removed to
maintain electrical neutrality. One of the sides is occupied bySr​2+ ​ions and other remain vacant.

The process of adding impurities to the crystalline is called doping.

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ELECTRICAL PROPERTIES OF SOLIDS

Apart from general physical characteristics like density and rigidity, solids depict another important
property called Conductivity. Conductivity is defined as the measure of a solid to ease the flow of
electrons and conduct electricity. The values of conductivity are diverged and vary from 10​-20​ to 10​-7​. The
unit of conductivity is ohm-1 m-1.

TYPES OF SOLIDS
On the basis of conductivity solids are classified into three types, namely:
● Conductors
● Insulators
● Semiconductors

CONDUCTORS
The solids which allow current to flow through them very easily are called Conductors. The
conductivity of solids lies between 10​4​ to 10​7​ ohm-1m-1. Metals are generally good conductors of
electricity as their conductivity is generally near to 10​7​ ohm-1 m-1.

INSULATORS
The solids which don’t allow electricity to flow through them are called Insulators. The conductivity
of insulators is majorly low with the range of 10​-20​ to 10​-10​ ohm-1 m-1. Some common examples of
insulators are plastics, rubber, wood etc.

SEMICONDUCTORS
The solids in which the value of conductivity lies between that of conductors and insulators are
known as Semiconductors. They neither allow complete electricity to pass through them and neither
resists the flow of electrons entirely. The value of conductivity lies between 10​-6​ to 10​4​ ohm-1 m-1. Some
good examples of semiconductors are as follows:
● Silicon
● Germanium
● Selenium

BAND THEORY
​Conduction
The process through which transfer of heat or electricity takes place inside a material due to the potential
difference between the end points is called Conduction. In solids conduction can be seen in two ways:
● Conduction in Metals
● Conduction in Semiconductors
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Conduction In Metals
A conductor can conduct current in two ways either by the flow of electrons or by the flow of ions. In
metallic conductors, the flow of electric current is possible due to the flow of electrons and in electrolytes,
the same is possible due to the flow of ions.
Metals have the potential to conduct electricity in solid and molten phase. The value of conductivity
relies upon a number of valence electrons available per atom. The atomic orbitals of metal atoms are
responsible for forming molecular orbitals. The energy level of molecular orbitals is nearly same to form
bands. When the band is half-filled or partially filled the electrons can flow easily from one band to
another, thereby making the electron to flow under an applied electric field.
But in case the gap between the valence band and conduction band (also called unoccupied band)
is large the flow of electrons is just not possible. Summarizing the points, the drawn conclusions are:

● When the gap is high, electrons don’t jump from one band to another thereby the substance is
said to have low conductivity
● When the gap is low, electrons can easily move from one band to another thereby the substance
is said to have high conductivity

Conduction in Semiconductors
Taking the case of semiconductors, the gap between valence band and conduction band is small.
Due to this small gap, some electrons can easily jump from valence band to conduction band, thereby
showing some conductivity. Electrical conductivity is directly proportional to temperature as the electrons
get more energy to move from one band to another.

Semiconductors which are made from only one or pure semiconductors are called Intrinsic
Semiconductor. Some common examples of intrinsic semiconductors are silicon and germanium. Also,
the conductivity of an intrinsic semiconductor is very low and of no practical use. To make intrinsic
semiconductor applicable we increase its conductivity with the help of doping.

DOPING
The process of adding an adequate amount of impurity in a semiconductor to increase its
conductivity is called doping. Doping is done in two ways, namely:

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● By adding electron rich impurities
● By adding electron deficient impurities

​By Adding Electron Rich Impurities

Silicon and germanium are present in group 14 of the periodic table with four valence electrons each.
They can form four covalent bonds with other neighbor atoms. When we dope silicon and germanium
with electron rich impurities like Phosphorus P the five electrons present in P form bonds with Si and Ge.
One extra electron left becomes delocalized and is responsible for increasing conductivity of silicon and
germanium. The semiconductors from this type of doping are also called n-type semiconductors as the
conductivity is enhanced due to the addition of negatively charged species.

​By Adding Electron Deficient Impurities

When we dope silicon or germanium with electron deficient species like Boron (B) or Aluminium (Al) we
obtain p-type semiconductors. Out of four electrons present in silicon, three are used to form covalent
bonds with Boron and 1 electron is left unshared. The place where the missing fourth electron is located
is called Electron Vacancy or Electron Hole. An electron from nearby atoms comes and fulfills the
vacancy.

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Applications of p-type and n-type semiconductors
Semiconductors are used worldwide and have many practical applications. Some are as follows:
● Combinations of p-type and n-type semiconductors are used in manufacturing of electronic
components
● Diode which is a general combination is utilized as a rectifier
● Transistors which are used in detecting and amplifying sound signals are made by placing one
layer of semiconductor in between two similar semiconductor layers
● Photo diode is widely utilized in converting light energy into electrical energy

MAGNETIC PROPERTIES OF SOLIDS

The magnetic properties of different materials are studies in terms of their magnetic moments which
arise due to the orbital motion and spinning motion of the electron.
As electron is charged particle, the circular motion of the electric charge causes the electron to act as a
tiny electromagnet.
The magnetic moment of the magnetic field generated due to orbital motion of the electron is along
the axis of rotation.
The electron also possesses magnetic moment due to the spin which is directed along the spin axis.
Thus, magnetic moment of the electron is due to travelling in closed path (orbital motion) about
the nucleus and spinning on its axis.
For each electron spin magnetic moment is ±μB Where μB, Bohr Magneton is the fundamental unit of
magnetic moment and is equal to 9.27 × 10-24 em2.
The magnetic moment due to orbital motion is equal to Mlμ B where Ml is the magnetic quantum
number of the electron.

● As magnetic moment is a vector quantity, the net magnetic moment of an electron may be
represented by an arrow.
● Thus a material may be considered to contain a number of magnetic dipoles (similar to a bar
magnet with north and south poles).
● Due to the magnetic moment of the electrons different substances behave differently towards the
external applied magnetic field.

Based on the behaviour in the external magnetic field, the substances are divided into different
categories as explained below

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● Diamagnetic Substances:
Substances which are weakly repelled by the external magnetic fields are called diamagnetic field e.g.
TiO2, NaCl, benzene etc. Diamagnetic substances have all their electrons paired.

● Paramagnetic Substances​:
Substances which are weakly attracted by magnetic field are called paramagnetic substances. These
substances have permanent magnetic dipoles due to the presence of some species (atoms, ions or
molecules) with unpaired electron. The paramagnetic substances lose their magnetism in the absence of
magnetic field. For e.g. TiO, VO2 and CuO, O2, Cu+2, Fe+3 etc.

● Ferromagnetic Substances​:
Substances which show permanent magnetism even in the absence of the magnetic field are called
Ferromagnetic substances. e.g. Fe Ni. CO, CrO2 show Ferromagnetism. Such substances remain
permanently magnetised, once they have been magnetised. This type of magnetism arises due to
spontaneous alignment of magnetic moment due to unpaired electrons in the same direction.

Anti Ferromagnetic Substance

Substances which are expected to possess paramagnetism or Ferromagnetism on the basis of unpaired
electron but actually they posses zero net magnetic moment are called anti Ferromagnetic substances
e.g. MnO, Mn2O3, MnO2.
Anti Ferromagnetism is due to presence of equal number of magnetic moments in the opposite
direction.

Ferrimagnetic Substances
Substance which are expected to posses large magnetism on the basis of the unpaired electrons but
actually have small net magnetic moments are called Ferrimagnetic substances e.g. Fe3O3 .

PYROELECTRICITY
Pyroelectricity (from the two Greek words pyr meaning fire, and electricity) is a property of certain
crystals which are naturally electrically polarized and as a result contain large electric fields.
Pyroelectricity can be described as the ability of certain materials to generate a temporary voltage when
they are heated or cooled.The change in temperature modifies the positions of the atoms slightly within
the crystal structure, such that the polarization of the material changes. This polarization change gives
rise to a voltage across the crystal. If the temperature stays constant at its new value, the pyroelectric
voltage gradually disappears due to leakage current. (The leakage can be due to electrons moving
through the crystal, ions moving through the air, or current leaking through a voltmeter attached across
the crystal.)

The most important example is gallium nitride ( GaN) semiconductor.

the large electric fields in this material are unwanted for light emitting diodes but are very helpful for the
fabrication of power transistors alternatively by electricity is interpreted as the ability of certain materials
to generate a temporary voltage when they are heated or cooled.

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