The Solid State

Amorphous and Crystalline Solids & Classification of Crystalline Solids

Amorphous and Crystalline Solids

• Based on the nature of the order of arrangement of the constituent particles, solids are classified as
amorphous and crystalline.

• Differences between amorphous and crystalline solids are listed in the given table.

Amorphous solids Crystalline solids

1 Have irregular shape 1 Have definite characteristic geometrical shape

2 Have only short-range order in the 2 Have long-range order in the arrangement of
arrangement of constituent constituent particles
particles

3 Gradually soften over a range of 3 Have sharp and characteristic melting point
temperature

4 When cut with a sharp-edged tool, 4 When cut with a sharp-edged tool, they split
they cut into two pieces with into two pieces with plain and smooth newly
irregular shapes generated surfaces.

5 Do not have definite heat of fusion 5 Have definite and characteristic heat of fusion

6 Isotropic in nature 6 Anisotropic in nature

 7 Pseudo solids or super-cooled 7 True solids
liquids

Classification of Crystalline Solids

• Based on the nature of intermolecular forces, crystalline solids are classified into four categories −

• Molecular solids

• Ionic solids

• Metallic solids

• Covalent solids

• Constituent particles are molecules

• Ionic solids

• Constituent particles are ions

• Hard but brittle
• Insulators of electricity in solid state, but conductors in molten state and in aqueous solution
• High melting point
• Attractive forces are Coulombic or electrostatic
• Example − NaCl, MgO, ZnS

• Metallic solids

• In metallic solids, positive ions are surrounded and are held together in a sea of delocalised
electrons.
• Hard but malleable and ductile
• Conductors of electricity in solid state as well as molten state
• Fairly high melting point
• Particles are held by metallic bonding
• Example − Fe, Cu, Mg

• Covalent or network solids

• Constituent particles are atoms

• Hard (except graphite, which is soft)
• Insulators of electricity (except graphite, which is a conductor of electricity)
• Very high melting point and can decompose before melting
• Particles are held by covalent bonding
• Example − SiO2 (quartz), SiC, diamond, graphite

Add to your knowledge

The property by virtue of which two or more crystalline solids having similar chemical
composition exist in the same crystalline form is called isomorphism. For example: Na3PO4.

The property by virtue of which a particular substance exists in more than one crystalline
form is called polymorphism. For example: existence of calcium carbonate in two crystalline
forms called calcite and aragonite.

Crystal Lattices and Unit Cells

Crystal Lattice

• Regular three-dimensional arrangement of points in space

• There are 14 possible three-dimensional lattices, known as Bravais lattices.

• Characteristics of a crystal lattice:

• Each point in a lattice is called lattice point or lattice site.

• Each lattice point represents one constituent particle (atom, molecule or ion).

• Lattice points are joined by straight lines to bring out the geometry of the lattice.

Unit Cell

• Smallest portion of a crystal lattice which, when repeated in different directions, generates the
entire lattice

• Characterised by −

(i) Its dimensions along the three edges a, b and c

(ii) Angles between the edges α, β and γ

• The unit cells can be classified as follows:

Seven Crystal Systems

There are seven types of primitive unit cells, as given in the following table.

The given table lists seven primitive unit cells and their possible variations as centered unit cells.
 Possible Types of
Crystal Class Axial Distances Axial Angles Examples
Unit Cells

Primitive, body-
1. Cubic a=b=c α = β = γ = 90° KCl, NaCl
centred, face-centred

Primitive, body-
2. Tetragonal a=b≠c α = β = γ = 90° SnO2, TiO2
centred

Primitive, body-
3. Orthorhombic a≠b≠c α = β = γ = 90° centred, face-centred, KNO3, BaSO4
end-centred

α = β = 90°; γ =
4. Hexagonal a=b≠c Primitive Mg, ZnO
120°

5. Trigonal (CaCO3) Calcite,

a=b=c α = β = γ ≠ 90° Primitive
or Rhombohedral HgS (Cinnabar)

α=γ= Primitive and end- Monoclinic sulphur,

6. Monoclinic a≠b≠c
90°; β ≠ 90° centred Na2SO4.10H2O

7. Triclinic a≠b≠c α ≠ β ≠γ≠ 90° Primitive K2Cr2O7, H3BO3

• Unit cells of 14 types Bravais lattices:

• Cubic lattices: All sides are of the same length, and the angles between the faces are 90° each
• Tetragonal lattices: One side is different in length from the other two, and the angles between the
faces are 90° each

• Orthorhombic lattices: Unequal sides; angles between the faces are 90° each

• Monoclinic lattices: Unequal sides; two faces have angles not equal to 90°

• Hexagonal lattice: One side is different in length from the other two, and the marked angles on two
faces are 60°

• Rhombohedral lattice: All sides are of equal length, and the marked angles on two faces are less
than 90°

• Triclinic lattice: Unequal sides; unequal angles, with none equal to 90°
 Questions asked in previous years’ board examinations

Ques. Name the type of structure possessed by a unit cell of CsCl.

(1 mark)

−2004 CBSE Delhi

Sol: A unit cell of CsCl possesses body-centred cubic structure.

Number of Atoms in a Unit Cell

Calculation of number of atoms in a unit cell

The number of atoms in a unit cell can be calculated, by using the following approximations.

An atom at the corner is shared by 8 unit cells. Hence, an atom at the corner contributes 1/8 to
the unit cell.

An atom at the face is shared by 2 unit cells. Hence, an atom at the face contributes 1/2 to the
unit cell.

An atom within the body of a unit cell is shared by no other unit cell. Hence, an atom at the
body contributes singly, i.e., 1 to the unit cell.

Primitive Cubic Unit Cell

Open structure for a primitive cubic unit cell is shown in the given figure.
Actual portions belonging to one unit cell are shown in the given figure.

Total number of atoms in one unit cell

Let us see the packing in a simple cubic unit cell through this video.

Body-Centred Cubic Unit Cell

Open structure for a body-centred cubic unit cell is shown in the given figure.

Actual portions belonging to one unit cell are shown in the given figure.
Total number of atoms in one unit cell

= 8 corners per corner atom + 1 body-centre atom

Face-Centred Cubic Unit Cell

Open structure for a face-centred cubic unit cell is shown in given figure.

Actual portions of atoms belonging to one unit cell are shown in the given figure.

Total number of atoms in one unit cell

= 8 corner atoms atom per unit cell + 6 face-centred atoms atom per unit cell

Now, let us visualise the packing in face-centred cubic lattice through this video.
 Questions asked in previous years’ board examinations

Ques. What is the total number of atoms per unit cell in a face-centred cubic (fcc) structure?

(1 mark)

−2008 CBSE Delhi

Sol: The total number of atoms per unit cell in a face-centred cubic (fcc) structure is 4 (8 corner

atoms atom per unit cell + 6 face-centred atoms atom per unit cell)

Ques. What is the number of atoms per unit cell in a body-centred cubic structure?

(1 mark)

−2007 CBSE Delhi

Sol: The number of atoms per unit cell in a body-centred cubic structure is 2 (8 corner atoms ×
atom per unit cell + 1 body-centre atom).

Closed-Packed Structures

Coordination number − The number of nearest neighbours of an atom

Close-Packing in One dimension

• Only one way of arrangement, i.e., the particles are arranged in a row, touching each other

• Coordination number = 2

Close-Packing in Two Dimensions

• Square close-packing in two dimensions

• AAA type arrangement

• The particles in the second row are exactly above those in the first row.

• Coordination number = 4

• Hexagonal close-packing in two dimensions

• ABAB type arrangement

• The particles in the second row are fitted in the depressions of the first row. The particles in the
third row are aligned with those in the first row.

• More efficient packing than square close-packing

• Coordination number = 6

Close-Packing in Three Dimensions

Three-dimensional close-packing is obtained by stacking two-dimensional layers (square close-

packed or hexagonal close-packed) one above the other.

• By stacking two-dimensional square close-packed layers

• The particles in the second layer are exactly above those in the first layer.

• AAA type pattern

• The lattice generated is simple cubic lattice, and its unit cell is primitive cubic unit cell.
• Coordination number = 6

• By stacking two-dimensional hexagonal close-packed layers

• Placing the second layer over the first layer

• The two layers are differently aligned.

• Tetrahedral void is formed when a particle in the second layer is above a void of the first layer.

• Octahedral void is formed when a void of the second layer is above the void of the first layer.

Here, T = Tetrahedral void, O = Octahedral void

Number of octahedral voids = Number of close-packed particles

Number of tetrahedral voids = 2 × Number of close-packed particles

• Placing the third layer over the second layer: There are two ways −

• Covering tetrahedral voids: ABAB … pattern. The particles in the third layer are exactly aligned
with those in the first layer. It results in a hexagonal close-packed (hcp) structure. Example:
Arrangement of atoms in metals like Mg and Zn
• Covering octahedral voids: ABCABC … octahedral voids. The particles in the third layer are not
aligned either with those in the first layer or with those in the second layer, but with those in the
fourth layer aligned with those in the first layer. This arrangement is called ‘C’ type. It results in
cubic close-packed (ccp) or face-centred cubic (fcc) structure. Example: Arrangement of atoms in
metals like Cu and Ag

• Coordination number in both hcp ad ccp structures is 12.

• Both hcp and ccp structures are highly efficient in packing (packing efficiency = 74%)

Questions asked in previous years’ board examinations

 Ques. What is the coordination number of each type of ions in a rock-salt type crystal
structure?

(1 mark)

−2008 CBSE Delhi

Sol: In rock salt or common salt, every Na+ ion is surrounded by 6 Cl− ions and each
Cl− ion is surrounded by 6 Na+ ions. Thus, the coordination number of each type of ion in
rock salt is 6.

Ques.What is the maximum possible coordination number of an atom in an hcp crystal

structure of an element?

(1 mark)

−2005 CBSE Delhi

Sol: The maximum possible coordination number of an atom in an hcp crystal structure
of an element is 12.

Formula of a Compound and Number of Voids Filled

• Number of octahedral voids = Number of close-packed particles

Number of tetrahedral voids = 2 × Number of close-packed particles

• In ionic solids, the bigger ions (usually anions) form the close-packed structure and the smaller
ions (usually cations) occupy the voids.

• If the latter ion is small enough, then it occupies the tetrahedral void, and if bigger, then it occupies
the octahedral void.

• Not all the voids are occupied. Only a fraction of the octahedral or tetrahedral voids are occupied.

• The fraction of the octahedral or tetrahedral voids that are occupied depends on the chemical
formula of the compound.

Example
 A compound is formed by two elements X and Y. The atoms of

element X formhcp lattice and those of element Y occupy th of the

tetrahedral voids. What is the formula of the compound formed?

Solution:

It is known that the number of tetrahedral voids formed is equal to

twice the number of atoms of element X.

It is given that only of the tetrahedral voids are occupied by the

atoms of element Y.

Therefore, ratio of the number of atoms of X and Y =

= 2: 1

Hence, the formula of the compound formed is X2Y.

Locating Tetrahedral Voids

• A unit cell of ccp or fcc lattice is divided into eight small cubes. Then, each small cube has 4 atoms at
alternate corners. When these are joined to each other, a regular tetrahedron is formed.

• This implies that one tetrahedral void is present in each small cube. Therefore, a total of eight
tetrahedral voids are present in one unit cell.
• Since each unit cell of ccp structure has 4 atoms, the number of tetrahedral voids is twice the
number of atoms.

Locating Octahedral Voids

• When the six atoms of the face centres are joined, an octahedron is generated. This implies that the
unit cell has one octahedral void at the body centre.

• Besides the body centre, there is one octahedral void at the centre of each of the 12 edges. But

only of each of these voids belongs to the unit cell.

• Now, the total number of octahedral voids in a cubic loose-packed structure

This means that in ccp structure, the number of octahedral voids is equal to the number of atoms in
each unit cell.
Now, let us see the stacking of two layers and the formation of the two types of voids by means of
this video.

Add to your knowledge

In NaCl, the Na+ ions occupy all the octahedral voids. In ZnS, Zn2+ are in
alternate tetrahedral voids. In CaF2, F- ions occupy all the tetrahedral voids.

In Fe3O4, if Fe2+ ions are replaced by divalent cations such as Mg2+ and Zn2+, then
the compounds obtained are called ferrites.

Questions asked in previous years’ board examinations

Ques. A cubic solid is made of two elements X and Y. Atoms Y are at the corners
of the cube and X at the body centre. What is the formula of the compound?

(1 mark)

−2006 CBSE Delhi

Sol: The atom at the body centre makes a contribution of 1 to the unit cell, while

the atom at the corner makes a contribution of to the unit cell.

Thus, number of atoms Y per unit cell

= Number of atoms × Contribution per unit cell

= 8 (at the corners) × atoms per unit cell

=1

Thus, number of atoms X per unit cell

= Number of atoms × contribution per unit cell

= 1 (at the body centre) × 1

 =1

Thus, the formula of the given compound is XY.

Packing Efficiency & Calculations Involving Unit Cell Dimensions

Packing Efficiency

• Percentage of total space filled by particles

Calculations of Packing Efficiency in Different Types of Structures

• Simple cubic lattice

In a simple cubic lattice, the particles are located only at the corners of the cube and touch each
other along the edge.

Let the edge length of the cube be ‘a’ and the radius of each particle be r.

Then, we can write:

a = 2r

Now, volume of the cubic unit cell = a3

= (2r)3

= 8r3

The number of particles present per simple cubic unit cell is 1.

 Therefore, volume of the occupied unit cell

Hence, packing efficiency

• Body-centred cubic structures

It can be observed from the above figure that the atom at the centre is in contact with the other two
atoms diagonally arranged.

From ΔFED, we have

From ΔAFD, we have

Let the radius of the atom be r.

Length of the body diagonal, c = 4r

or,

Volume of the cube,

A body-centred cubic lattice contains 2 atoms.

• hcp and ccp Structures

Let the edge length of the unit cell be ‘a’ and the length of the face diagonal AC be b.

From ΔABC, we have

Let r be the radius of the atom.

Now, from the figure, it can be observed that:

Now, volume of the cube,

We know that the number of atoms per unit cell is 4.

• Thus, ccp and hcp structures have maximum packing efficiency.

Calculations Involving Unit Cell Dimensions

In a cubic crystal, let

a = Edge length of the unit cell

d = Density of the solid substance

M = Molar mass of the substance

Then, volume of the unit cell = a3

Again, let

z = Number of atoms present in one unit cell

m = Mass of each atom

Now, mass of the unit cell = Number of atoms in the unit cell × Mass of each atom

=z×m

But, mass of an atom, m

Therefore, density of the unit cell,

Let us calculate the density of an element crystallising in face-centred cubic lattice.

Questions asked in previous years’ board examinations

Ques. The density of copper metal is 8.95 g cm−3. If the radius of copper atom is 127.8 pm,
is the copper unit cell a simple cubic, a body-centred cubic or a face centred cubic
structure? (Given: At. Mass of Cu = 63.54 g mol−1 and NA = 6.02 × 1023 mol−1)

(3 marks)

−2010 CBSE Delhi

Sol: We know that density,

For SCC: z = 1 and a = 2r

For BCC: z = 2 and

For FCC: z = 4 and

Substituting the values of z and a in equation (i) we can calculate the value of density.

It is given that M = 63.54 g mol−1

NA = 6.02 × 1023 mol−1

r = 127.8 × 10−10 cm
The given value of density is 8.95 g/cm3. Hence, from the given data, we can conclude that
copper unit cell is face centred cubic or fcc.

Ques. Iron has a body-centred cubic unit cell with a cell edge of 286.65 pm. The density of
iron is 7.87 g cm−3. Use this information to calculate Avogadro’s number.

(At. Mass of Fe = 56 g mol−1)

(3 marks)

−2009 CBSE Delhi

Sol: In a body-centred cubic unit cell, number of atoms present = 2

At mass of iron = 56 g mol−1

Density of iron = 7.87 g cm−3

Mass of iron = 7.87 × Volume

Volume in BCC = (a)3

= (286.65)3 pm
= 2.34 × 10−23 cm

Mass = 7.87 × 2.34 × 10−23 g

∴ Avogadro’s number = 6.022 × 1023

Ques. An element has a body-centred cubic structure with a cell edge of 288 pm. The
density of the element is 7.2 g cm−3 Calculate the number of atoms presents in 208 g of the
element.

(3 marks)

−2006 CBSE Delhi

Sol: Cell edge (a) = 288 pm

Volume of unit cell = a3

= (288 pm)3

= (288 × 10−10 cm)3

= 2.389 × 10−23 cm3

Volume of 208 g of the element =

= 28.89 cm3

Number of unit cells =

= 12.09 × 1023

In a bcc structure, the number of atoms per unit cell = 2

∴ Number of atoms in 208 g of the given element = 2 × 12.09 × 1023

= 24.18 × 1023

Ques. Aluminium metal forms a cubic close-packed crystal structure. Its atomic radius is
125 x 10 -12 m.

(a) Calculate the length of the side of the unit cell.

(b) How many such unit cells are there in 1.00 m3 of aluminium?

(3 marks)

−2005 CBSE Delhi

Soli:

(a) For a cubic close-packed crystal structure,

Radius of an atom,

Where, a → Edge length

Therefore, a =

Hence, the length of the side of the unit cell is 354 × 10−12 m.

(b) Volume of the unit cell = a3

Ques. Calculate the density of silver which crystallises in the face-centred cubic structure.
The distance between the nearest silver atoms in this structure is 287 pm.

(3 marks)

−2004 CBSE Delhi

Sol: Given, molar mass of Ag, M = 107.87 g mol−1

NA = 6.02 × 1023 mol−1

In case of fcc lattice, number of atoms per unit cell, z = 4

Distance between two nearest Ag atoms = 287 pm

Thus, edge length = 406 pm (approx)

= 406 × 10−12 m

Therefore, density of silver is given by

 Imperfections in Solids

Defects

• Irregularities or deviations from the ideal arrangement of constituent particles

Two types:

• Point defects − Irregularities in the arrangement of constituent particles around a point or an atom
in a crystalline substance.

• Line defects − Irregularities in the arrangement of constituent particles in entire rows of lattice
points.

• These irregularities are called crystal defects.

Types of Point Defects

Three types:

• Stoichiometric defects

• Impurity defect

• Non-stoichiometric defects

Stoichiometric Defects

• Do not disturb stoichiometry of the solid

• Also called intrinsic or thermodynamic defects

• Two types −
(i) Vacancy defect
(ii) Interstitial defect

• Vacancy defect

• When some of the lattice sites are vacant

• Shown by non-ionic solids

• Created when a substance is heated

• Results in the decrease in density of the substance

• Interstitial defect

• Shown by non-ionic solids

• Created when some constituent particles (atoms or molecules) occupy an interstitial site of the
crystal.

• Ionic solids show these two defects as Frenkel defect and Schottky defect.

• Frenkel defect

• Shown by ionic solids containing large differences in the sizes of ions

• Created when the smaller ion (usually cation) is dislocated from its normal site to an interstitial
site

• Creates a vacancy defect as well as an interstitial defect

• Also known as dislocation defect

• Ionic solids such as AgCl, AgBr, AgI and ZnS show this type of defect.

• Schottky defect

• Basically a vacancy defect shown by ionic solids

• An equal number of cations and anions are missing to maintain electrical neutrality

• Results in the decrease in the density of the substance

• Significant number of Schottky defect is present in ionic solids. For example, in NaCl, there are
approximately 106 Schottky pairs per cm3, at room temperature.

• Shown by ionic substances containing similar-sized cations and anions; for example, NaCl, KCl CsCl,
AgBr

Impurity Defect

• Point defect due to the presence of foreign atoms

• For example, if molten NaCl containing a little amount of SrCl2 is crystallised, some of the sites of
Na+ ions are occupied by Sr2+ ions. Each Sr2+ ion replaces two Na+ ions, occupying the site of one
ion, leaving the other site vacant. The cationic vacancies thus produced are equal in number to
those of Sr2+ ions.
• Solid solution of CdCl2 and AgCl also shows this defect

Non-Stoichiometric Defects

• Result in non-stoichiometric ratio of the constituent elements

• Two types −

• Metal excess defect

• Metal deficiency defect

Metal excess defect

• Metal excess defect due to anionic vacancies:

• Alkali metals like NaCl and KCl show this type of defect.

• When crystals of NaCl are heated in an atmosphere of sodium vapour, the sodium atoms are
deposited on the surface of the crystal. The Cl− ions diffuse from the crystal to its surface and
combine with Na atoms, forming NaCl. During this process, the Na atoms on the surface of the
crystal lose electrons. These released electrons diffuse into the crystal and occupy the vacant
anionic sites, creating F-centres.

• When the ionic sites of a crystal are occupied by unpaired electrons, the ionic sites are called F-
centres.
• Metal excess defect due to the presence of extra cations at interstitial sites:

• When white zinc oxide is heated, it loses oxygen and turns yellow.

Then, zinc becomes excess in the crystal, leading the formula of the oxide to . The
excess Zn ions move to the interstitial sites, and the electrons move to the neighbouring
2+

interstitial sites.

Metal deficiency defect

• Arises when a solid contains lesser number of cations compared to the stoichiometric proportion.

• For example, FeO is mostly found with a composition of . In crystals of FeO, some Fe2+ ions
are missing, and the loss of positive charge is made up by the presence of the required number
of Fe3+ ions.

Questions asked in previous years’ board examinations

Ques. Which point defect in crystals of a solid decreases the density of the solid?

(1 mark)

−2010 CBSE Delhi

Sol: Vacancy defect decreases the density of a substance. Vacancy defect in ionic solids
is known as Schottky defect.

Ques. Which point defect in crystals does not affect the density of the relevant solid?

(1 mark)
 2009 CBSE Delhi

Sol: Frenkel defect in crystals does not affect the density of the relevant solid.

Ques. Which point defect in its crystal units alters the density of a solid?

(1 mark)

2008 CBSE Delhi

Sol: Schottky defect in crystals units alters the density of a solid.

Ques. How would you account for the following?

(i) Frenkel defects are not found in alkali metal halides.

(ii) Schottky defects lower the density of related solids.

(iii) Impurity doped silicon is a semiconductor.

(3 marks)

2008 CBSE Delhi

Sol: (i) Frenkel defects are shown by ionic solids having large differences in the sizes
of ions. Solids such as ZnS, AgCl show these defects due to the small size of Zn2+ and
Ag+ ions, and the large size of anions. Alkali metals are not so small so as to show these
defects. Hence, Frenkel defects are not found in alkali metal halides.

(ii) Schottky defects are basically vacancy defects in ionic solids. In these defects,
lattice sites become vacant. As a result, the density of the substance decreases.

(iii) Silicon is an intrinsic semi-conductor in which conductivity is very low. To

increase its conductivity, silicon is doped with an appropriate amount of suitable
impurity. When doped with electron-rich impurities such as P or As, n-type semi-
conductor is obtained, and when doped with electron-deficient impurities, p-type
semi-conductor is obtained. In n-type semiconductor, negatively charged electron is
responsible for increasing conductivity, and in p-type semiconductor, electron hole is
responsible for increasing conductivity.

Ques. What are the types of lattice imperfections found in crystals?

(1 mark)
 2004 CBSE Delhi

Sol: Two types of lattice imperfections are found in crystals.

(i) Point defects (irregularities in arrangement around a point or an atom)

(ii) Line defects (irregularities in arrangement in entire rows of lattice points)

Ques. Explain interstitial defect with examples.

(3 marks)

2004 CBSE Delhi

Sol:Interstitial defect is shown by non-ionic solids. This type of defect is created when
some constituent particles (atoms or molecules) occupy an interstitial site of the
crystal. The density of a substance increases because of this defect.

Electrical Properties

Conduction of Electricity in Metals

• Metals conduct electricity in molten state.

• The conductivity of metals depends upon the number of valence electrons.

• In metals, the valence shell is partially filled, so this valence band overlaps with a higher energy
unoccupied conduction band so that electrons can flow easily under an applied electric field.

• In the case of insulators, the gap between filled valence shell and the next higher unoccupied band
is large so that electrons cannot jump from the valence band to the conduction band.
 Conduction of Electricity in Semiconductors

• The gap between the valence band and conduction band is so small that some electrons may jump
to the conduction band.

• Electrical conductivity of semiconductors increases with increase in temperature.

• Substances like Si, Ge show this type of behaviour, and are called intrinsic semiconductors.

• Doping − Process of adding an appropriate amount of suitable impurity to increase conductivity

• Doping is done with either electron-rich or electron-deficient impurity as compared to the intrinsic
semiconductor Si or Ge.

• There are two types of semiconductors:

1. n − type semiconductor

2. p − type semiconductor

• n − type semiconductor

• Conductivity increases due to negatively charged electrons

• Generated due to the doping of the crystal of a group 14 element such as Si or Ge, with a group 15
element such as P or As
• p − type semiconductor

• Conductivity increases as a result of electron hole

• Generated due to the doping of the crystal of a group 14 element such as Si or Ge, with a group 13
element such as B, Al or Ga

• Applications of n − type and p − type semiconductors

• In making a diode, which is used as a rectifier

• In making transistors, which are used for detecting or amplifying radio or audio signals

• In making a solar cell, which is a photo diode used for converting light energy into electrical energy
• A large number of compounds (solid) have been prepared by the combination of groups 13 and 15
or 12 and 16 to stimulate average valence of four as in Si or Ge.

• Examples of compounds of groups 13 − 15 are InSb, AlP, GaAs

• Examples of compounds of groups 12 − 16 are ZnS, CdS, CdSe, HgTe

• Some transition metal oxides like TiO, CrO2, ReO3 behave like metals.

• For example, ReO3 resembles metallic copper in its conductivity and appearance

• Some oxides like VO, VO2, VO3, TiO3 show metallic or insulating properties depending on
temperature.

Do you know?

Polyacetylene, an organic compound shows conductivity when exposed to iodine

vapours.

Questions asked in previous years’ board examinations

Ques. What is semiconductor? Describe the two main types of semiconductors and
explain mechanisms for their conduction.

(3 marks)

−2008 CBSE Delhi

Sol: Solids having intermediate conductivities (from 10−6 to 104 Ω−1 m−1) are
calledsemiconductors. Germanium and silicon are two examples of semi-conductors.
These substances act as insulators at low temperatures and as conductors at high
temperatures. There are two types of semiconductors:

1. n-type semiconductor:

When the crystal of a semiconductor is doped with group-15 elements (P, As, Sb or Bi),
only four of the five valence electrons of the doped atoms participate in forming covalent
bonds with the atoms of the semiconductors. The fifth electron is free to conduct
 electricity. As these crystals contain extra electrons, these are known as n-type
semiconductors.

2. p-type semiconductor:

When the crystal of a semiconductor is doped with group-13 elements (Al, Ga or In), only
three covalent bonds are formed by the atoms of the doped atoms as they contain three
valence electrons. A hole is created at the place where the electron is absent. The
presence of such holes increases the conductivity of the semiconductor as the
neighbouring electrons can move into these holes, thereby creating newer holes. As these
crystals contain lesser electrons than un-doped crystals, they are known as p-type
semiconductors.

Magnetic Properties

• Each electron in an atom behaves like a tiny magnet.

• The magnetic moment of an electron originates from its two types of motion.

• Orbital motion around the nucleus

• Spin around its own axis

• Thus, an electron has a permanent spin and an orbital magnetic moment associated with it.

• An orbiting electron

• A spinning electron

• Based on magnetic properties, substances are classified into five categories −

• Paramagnetic

• Diamagnetic

• Ferromagnetic

• Ferrimagnetic

• Anti-ferromagnetic

Paramagnetism

• The substances that are attracted by a magnetic field are called paramagnetic substances.

• Some examples of paramagnetic substances are O2, Cu2+, Fe3+ and Cr3+.

• Paramagnetic substances get magnetised in a magnetic field in the same direction, but lose
magnetism when the magnetic field is removed.

• To undergo paramagnetism, a substance must have one or more unpaired electrons. This is
because the unpaired electrons are attracted by a magnetic field, thereby causing paramagnetism.

Diamagnetism

• The substances which are weakly repelled by magnetic field are said to have diamagnetism.

• Example − H2O, NaCl, C6H6

• Diamagnetic substances are weakly magnetised in a magnetic field in opposite direction.

• In diamagnetic substances, all the electrons are paired.

• Magnetic characters of these substances are lost due to the cancellation of moments by the pairing
of electrons.

Ferromagnetism

• The substances that are strongly attracted by a magnetic field are called ferromagnetic substances.

• Ferromagnetic substances can be permanently magnetised even in the absence of a magnetic field.

• Some examples of ferromagnetic substances are iron, cobalt, nickel, gadolinium and
CrO2.

• In solid state, the metal ions of ferromagnetic substances are grouped together into small regions
called domains, and each domain acts as a tiny magnet. In an un-magnetised piece of a
 ferromagnetic substance, the domains are randomly oriented, so their magnetic moments get
cancelled. However, when the substance is placed in a magnetic field, all the domains get oriented
in the direction of the magnetic field. As a result, a strong magnetic effect is produced. This
ordering of domains persists even after the removal of the magnetic field. Thus, the ferromagnetic
substance becomes a permanent magnet.

• Schematic alignment of magnetic moments in ferromagnetic substances is as follows:

Ferrimagnetism

• The substances in which the magnetic moments of the domains are aligned in parallel and anti-
parallel directions, in unequal numbers, are said to have ferrimagnetism.

• Examples include Fe3O4 (magnetite), ferrites such as MgFe2O4 and ZnFe2O4.

• Ferrimagnetic substances are weakly attracted by a magnetic field as compared to ferromagnetic

substances.

• On heating, these substances become paramagnetic.

• Schematic alignment of magnetic moments in ferrimagnetic substances is as follows:

Anti-ferromagnetism

• Antiferromagnetic substanceshave domain structures similar to ferromagnetic substances, but are

oppositely oriented.

• The oppositely oriented domains cancel out each other’s magnetic moments.

• Schematic alignment of magnetic moments in anti-ferromagnetic substances is as follows:

Do you know?

When a substance offers no resistance to the flow of electric current, it is said to be

superconducting. This phenomenon was first discovered by Kammerlingh Onnes.

Questions asked in previous years’ board examinations

Ques. What type of substances exhibits antiferromagnetism?

(1 mark)

−2008 CBSE Delhi

Sol: Antiferromagnetism is exhibited by substances which have domain structure similar to

ferromagnetic substances, but are oppositely oriented (thereby cancelling out each other’s
magnetic moment), e.g., MnO.

Ques. Explain each of the following with a suitable example:

(i) Paramagnetism

(ii) Piezoelectric effect

(3 marks)

−2007 CBSE Delhi

Sol: (i) Paramagnetism:

The phenomenon due to which a substance gets attracted towards a magnetic field is called
paramagnetism. The substances attracted by a magnetic field are called paramagnetic
substances. Some examples of paramagnetic substances are O2, Cu2t, Fe3t and Cr3t.

Paramagnetic substances get magnetised in a magnetic field in the same direction, but lose
magnetism when the magnetic field is removed. To undergo paramagnetism, a substance
must have one or more unpaired electrons. This is because the unpaired electrons are
attracted by a magnetic field, thereby causing paramagnetism.

(ii) Piezoelectric effect:

The production of electricity due to the displacement of ions, on the application of

mechanical stress, or the production of mechanical stress and/or strain due to atomic
displacement, on the application of an electric field is known as piezoelectric effect.
Piezoelectric materials are used in transducers − devices that convert electrical energy into
mechanical stress/strain or vice-versa. Some piezoelectric materials are lead-zirconate
(PbZrO3), ammonium dihydrogen phosphate (NH4H2PO4), quartz, etc.

Ques. What makes alkali metal halides sometimes coloured, which are otherwise colourless?

(1 mark)

−2004 CBSE Delhi

Alkali metal halides have anionic sites occupied by unpaired electrons. These are called F-
centres, and impart colour to the crystals of alkali metal halides. For example, the excess of
lithium in LiCl makes it pink.