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Unit 1 Solid State
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 constituent
arrangement of constituent particles particles

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

4 When cut with a shape-edged tool, they cut 4 When cut with a shape-edged tool, they split into two
into two pieces with irregular shapes pieces with plain and smooth newly 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 liquids 7 True solids

Classification of Crystalline Solids
 Based on the nature of intermolecular forces, crystalline solids are classified into four categories −
o Molecular solids
o Ionic solids
o Metallic solids
o Covalent solids
 Molecular solids
o Constituent particles are molecules

 Ionic solids
o Constituent particles are ions
o Hard but brittle
o Insulators of electricity in solid state, but conductors in molten state and in aqueous solution
o High melting point
o Attractive forces are Coulombic or electrostatic
o Example − NaCl, MgO, ZnS

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 Metallic solids
o In metallic solids, positive ions are surrounded and are held together in a sea of delocalised electrons.
o Hard but malleable and ductile
o Conductors of electricity in solid state as well as molten state
o Fairly high melting point
o Particles are held by metallic bonding
o Example − Fe, Cu, Mg
 Covalent or network solids
o Constituent particles are atoms
o Hard (except graphite, which is soft)
o Insulators of electricity (except graphite, which is a conductor of electricity)
o Very high melting point
o Particles are held by covalent bonding
Example − SiO2 (quartz), SiC, diamond, graphite
Crystal Lattice
Regular three-dimensional arrangement of points in space is called crystal lattice
or space lattice.
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
It is characterised by −
(i) Its dimensions along the three edges a, b and c

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

Seven Crystal Systems

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

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

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

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

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

(CaCO3)
5. Trigonal or
a=b=c α = β = γ ≠ 90° Primitive Calcite, HgS
Rhombohedral
(Cinnabar)

Monoclinic
Primitive and end-
6. Monoclinic a≠b≠c α = γ = 90°; β ≠ 90° sulphur,
centred
Na2SO4.10H2O

K2Cr2O7,
7. Triclinic a≠b≠c α ≠ β ≠γ≠ 90° Primitive
H3BO3
 Unit cells of 14 types Bravais lattices:
o Cubic lattices: All sides are of the same length, and the angles between the faces are 90° each

o Tetragonal lattices: One side is different in length from the other two, and the angles between the
faces are 90° each

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o
o 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°

Number of Atoms in a Unit Cell

Primitive Cubic Unit Cell

Open structure for a primitive cubic unit cell Total number of atoms in one unit cell
is shown in the given figure.

Actual portions belonging to one unit cell

are shown in the given figure.

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Body-Centred Cubic Unit Cell

Open structure for a body-centred cubic unit Total number of atoms in one unit cell
cell is shown in the given figure.
= 8 corners per corner atom + 1 body-centre atom

Actual portions belonging to one unit cell are

shown in the given figure.

Face-Centred Cubic Unit Cell

Open structure for a face-centred cubic unit cell Total number of atoms in one unit cell
is shown in given figure.
= 8 corner atoms atom per unit cell + 6 face-

centred atoms atom per unit cell

Actual portions of atoms belonging to one unit

cell are shown in the given figure.

Closed-Packed Structures
Coordination number − The number of nearest neighbours of a particle
Close-Packing in One dimension
 Only one way of arrangement, i.e., the particles are arranged in a row, touching each other

o Coordination number = 2
Close-Packing in Two Dimensions
 Square close-packing in two dimensions
1. AAA type arrangement
2. The particles in the second row are exactly above those in the first row.
3. Coordination number = 4

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 Hexagonal close-packing in two dimensions

1. ABAB type arrangement
2. 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.
3. More efficient packing than square close-packing
4. 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.
(a) By stacking two-dimensional square close-packed layers
1. The particles in the second layer are exactly above those in the first layer.
2. AAA type pattern
3. The lattice generated is simple cubic lattice, and its unit cell is primitive
cubic unit cell.
4. Coordination number = 6

(b) By stacking two-dimensional hexagonal close-packed layers

(i) Placing the second layer over the first layer
1. The two layers are differently aligned.
2. Tetrahedral void is formed when a particle in the
second layer is above a void of the first layer.
3. 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

(ii) Placing the third layer over the second layer

There are two ways −
Covering tetrahedral voids: Covering octahedral voids:
ABAB … pattern. The particles in the third layer are ABCABC … octahedral voids. The particles in the third
exactly aligned with those in the first layer. It results in layer are not aligned either with those in the first layer or
a hexagonal close-packed (hcp) structure. Example: with those in the second layer, but with those in the fourth
Arrangement of atoms in metals like Mg and Zn 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.

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

 Both hcp and ccp structures are highly efficient in packing (packing efficiency = 74%)
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.
o 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 form hcp 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 Locating Octahedral Voids

1. When the six atoms of the face centres are joined, an

1. A unit cell of ccp or fcc lattice is octahedron is generated. This implies that the unit cell has one
divided into eight small cubes. Then, octahedral void at the body centre.
each small cube has 4 atoms at 2. Besides the body centre, there is one octahedral void at the
alternate corners. When these are
joined to each other, a regular centre of each of the 12 edges. But only of each of these
tetrahedron is formed. voids belongs to the unit cell.
2. 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.
3. Since each unit cell of ccp structure
has 4 atoms, the number of tetrahedral
voids is twice the number of atoms. 3. Now, the total number of octahedral voids in a cubic close-
packed structure

This means that in ccp structure, the number of octahedral

voids is equal to the number of atoms in each unit cell.

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Packing Efficiency
 Percentage of total space filled by particles
Calculations of Packing Efficiency in Different Types of Structures
1. 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 one particle

Hence, packing efficiency

2. 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.
Let the radius of the atom be r.
Length of the body diagonal, c = 4r

From ΔFED, we have

From ΔAFD, we have

or,

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Volume of the cube,

A body-centred cubic lattice contains 2 spheres.

So, volume occupied by two spheres in the unit cell

3. 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 spheres per unit cell is 4.

So, volume occupied by four spheres in the unit cell

= 74%
 Thus, ccp and hcp structures have maximum packing efficiency.
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Calculations Involving Unit Cell Dimensions

In a cubic crystal,
Let a = Edge length of the unit cell
Then, volume of the unit cell = a3

Again,
Let z = Number of atoms present in one unit cell
m = Mass of each atom
M = Molar mass of the substance
NA = Avogadro number
Now, mass of the unit cell = Number of atoms in the unit cell × Mass of each atom
=z×m
M M
=zx (  mass of an atom m = )
N A N A
mass of the unit cell
Therefore, density of the unit cell d =
volume of the unit cell
zXM
= 3
a XNA

Imperfections in Solids
Defects
 Irregularities or deviations from the ideal arrangement of constituent particles
 Two types:
o Point defects − Irregularities in the arrangement of constituent particles around a point or
an atom in a crystalline substance.
o 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:
o Stoichiometric defects
o Impurity defect
o 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
o When some of the lattice sites are vacant
o Shown by non-ionic solids
o Created when a substance is heated
o Results in the decrease in density of the substance

 Interstitial defect
o Shown by non-ionic solids
o Created when some constituent particles (atoms or
molecules) occupy an interstitial site of the crystal.

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 Ionic solids show these two defects as Frenkel defect and Schottky defect.
 Frenkel defect
o Shown by ionic solids containing large differences
in the sizes of ions
o Created when the smaller ion (usually cation) is
dislocated from its normal site to an interstitial site
o Creates a vacancy defect as well as an interstitial
defect
o Also known as dislocation defect
o Ionic solids such as AgCl, AgBr, AgI and ZnS show
this type of defect.

 Schottky defect
o Basically a vacancy defect shown by ionic solids
o An equal number of cations and anions are missing to
maintain electrical neutrality
o Results in the decrease in the density of the substance
o Significant number of Schottky defect is present in
ionic solids. For example, in NaCl there are
approximately106 Schottky pairs per cm3 at room
temperature. In 1 cm3 there are about 1022 ions. Thus,
there is one Schottky defect per 1016 ions.
o 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
(a) Metal excess defect due to anionic vacancies:
1. Alkali metals like NaCl and KCl show this type of defect.
2. 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.
3. 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 (from
the German word Farbenzenter for colour centre).
4. When the ionic sites of a crystal are occupied by unpaired electrons, the ionic sites are called F-
centres. They impart yellow colour to the crystals of NaCl. The colour results by excitation of these
electrons when they absorb energy from the visible light falling on the crystals. Similarly, excess of
lithium makes LiCl crystals pink and excess of potassium makes KCl crystals violet (or lilac).
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(b)Metal excess defect due to the presence of extra cations at interstitial sites:
1. When white zinc oxide is heated, it loses oxygen and turns yellow.

2. Then, zinc becomes excess in the crystal, leading the formula of

the oxide to .
3. The excess Zn ions move to the interstitial sites, and the electrons
2+

move to the neighbouring interstitial sites.

 Metal deficiency defect

o Arises when a solid contains lesser number of cations compared to the stoichiometric
proportion.
o For example, FeO is mostly found with a composition of . In crystals of FeO,
some Fe ions are missing, and the loss of positive charge is made up by the presence of
2+

the required number of Fe3+ ions.

Electrical Properties

Conduction of Electricity in Metals

 Metals conduct electricity in solid as well as molten state.
 The conductivity of metals depends upon the number of valence electrons.
 In metals, the valence bond is partially filled, or it 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
o 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:
i. n − type semiconductor
ii. p − type semiconductor
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 n − type semiconductor
o Conductivity increases due to negatively charged electrons
o 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
o Conductivity increases as a result of electron hole
o 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

o In making a diode, which is used as a rectifier
o In making transistors, which are used for detecting or amplifying radio or audio signals
o 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.
o Examples of compounds of groups 13 − 15 are InSb, AlP, GaAs
o Examples of compounds of groups 12 − 16 are ZnS, CdS, CdSe, HgTe
 Some transition metal oxides like TiO, CrO2, ReO3 behave like metals.
o For example, ReO3 resembles metallic copper in its conductivity and appearance
o Some oxides like VO, VO2, VO3, TiO3 show metallic or insulating properties depending
on temperature.

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.
o Orbital motion around the nucleus
o Spin around its own axis
 Thus, an electron has a permanent spin and an orbital magnetic moment associated with it.
o An orbiting electron
o A spinning electron

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

1. Paramagnetism
 The substances that are attracted by a magnetic field are called paramagnetic substances.
o 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.
2. Diamagnetism
 The substances which are weakly repelled by magnetic field are said to have diamagnetism.
o 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.
3. 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:

4. 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:

5. 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:

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CHAPTER END EXERCISE

Question 1.1:
Define the term 'amorphous'. Give a few examples of amorphous solids.
Answer
Amorphous solids are the solids whose constituent particles are of irregular shapes and have short range order. These
solids are isotropic in nature and melt over a range of temperature. Therefore, amorphous solids are sometimes called
pseudo solids or super cooled liquids. They do not have definite heat of fusion. When cut with a sharp-edged tool, they
cut into two pieces with irregular surfaces. Examples of amorphous solids include glass, rubber, and plastic.

Question 1.2:
What makes a glass different from a solid such as quartz? Under what conditions could quartz be converted into glass?
Answer
The arrangement of the constituent particles makes glass different from quartz. In glass, the constituent particles have
short range order, but in quartz, the constituent particles have both long range and short range orders.
Quartz can be converted into glass by heating and then cooling it rapidly.

Question 1.3:
Classify each of the following solids as ionic, metallic, molecular, network (covalent) or amorphous.
(i) Tetra phosphorus decoxide (P4O10) (ii) Ammonium phosphate (NH4)3PO4 (iii) SiC (iv) I2
(v) P4 (vi) Plastic (vii) Graphite (viii) Brass (ix) Rb (x) LiBr (xi) Si
 Answer
Ionic → (ii) Ammonium phosphate (NH4)3PO4, (x) LiBr
Metallic → (viii) Brass, (ix) Rb
Molecular → (i) Tetra phosphorus decoxide (P4O10), (iv) I2, (v) P4.
Covalent (network) → (iii) SiC, (vii) Graphite, (xi) Si
Amorphous → (vi) Plastic

Question 1.4:
(i) What is meant by the term 'coordination number'?
(ii) What is the coordination number of atoms:
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(a) in a cubic close-packed structure?

(b) in a body-centred cubic structure?
 Answer
(i) The number of nearest neighbours of any constituent particle present in the crystal lattice is called its coordination
number.
(ii) The coordination number of atoms
(a) in a cubic close-packed structure is 12, and
(b) in a body-centred cubic structure is 8

Question 1.5:
How can you determine the atomic mass of an unknown metal if you know its density and the dimension of its unit
cell? Explain.
 Answer
By knowing the density of an unknown metal and the dimension of its unit cell, the atomic mass of the metal can be
determined.
Let ‘a’ be the edge length of a unit cell of a crystal, ‘d’ be the density of the metal, ‘m’ be the atomic mass of the
metal and ‘z’ be the number of atoms in the unit cell.

Now, density of the unit cell

[Since mass of the unit cell = Number of atoms in the unit cell × Atomic mass]
[Volume of the unit cell = (Edge length of the cubic unit cell)3]
From equation (i), we have:

Now, mass of the metal (m)

Therefore,
If the edge lengths are different (say a, b and c), then equation (ii) becomes:

From equations (iii) and (iv), we can determine the atomic mass of the unknown metal.

Question 1.6:
'Stability of a crystal is reflected in the magnitude of its melting point'. Comment. Collect melting points of solid
water, ethyl alcohol, diethyl ether and methane from a data book. What can you say about the intermolecular forces
between these molecules?
 Answer
Higher the melting point, greater is the intermolecular force of attraction and greater is the stability. A substance with
higher melting point is more stable than a substance with lower melting point.
The melting points of the given substances are:
Solid water → 273 K
Ethyl alcohol → 158.8 K
Diethyl ether → 156.85 K
Methane → 89.34 K
Now, on observing the values of the melting points, it can be said that among the given substances, the intermolecular
force in solid water is the strongest and that in methane is the weakest.

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Question 1.7:
How will you distinguish between the following pairs of terms:
(i) Hexagonal close-packing and cubic close-packing?
(ii) Crystal lattice and unit cell?
(iii) Tetrahedral void and octahedral void?
 Answer
i. A 2-D hexagonal close-packing contains two types of triangular voids (a and b) as shown in
figure 1. Let us call this 2-D structure as layer A. Now, particles are kept in the voids present in
layer A (it can be easily observed from figures 2 and 3 that only one of the voids will be occupied
in the process, i.e., either a or b). Let us call the particles or spheres present in the voids of layer
A as layer B. Now, two types of voids are present in layer B (c and d). Unlike the voids present in
layer A, the two types of voids present in layer B are not similar. Void c is surrounded by 4
spheres and is called the tetrahedral void. Void d is surrounded by 6 spheres and is called the
octahedral void.

Figure 1

Figure 2 Figure 3
Now, the next layer can be placed over layer B in 2 ways.
Case 1: When the third layer (layer C) is placed over the second one (layer B) in such a manner
that the spheres of layer C occupy the tetrahedral voids c.
In this case we get hexagonal close-packing. This is shown in figure 4. In figure 4.1, layer B is present
over the voids a and layer C is present over the voids c. In figure 4.2, layer B is present over the voids b
and layer C is present over the voids c. It can be observed from the figure that in this arrangement, the
spheres present in layer C are present directly above the spheres of layer A. Hence, we can say that the
layers in hexagonal close-packing are arranged in an ABAB….. pattern.
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Figure 4.1 Figure 4.2

Case 2: When the third layer (layer C) is placed over layer B in such a manner that the spheres of
layer C occupy the octahedral voids d.
In this case we get cubic close-packing. In figure 5.1, layer B is present over the voids a and layer C is
present over the voids d. In figure 5.2, layer B is present over the voids b and layer C is present over the
voids d. It can be observed from the figure that the arrangement of particles in layer C is completely
different from that in layers A or B. When the fourth layer is kept over the third layer, the arrangement of
particles in this layer is similar to that in layer A. Hence, we can say that the layers in cubic close-packing
are arranged in an ABCABC….. pattern.

Figure 5.1 Figure 5.2

The side views of hcp and ccp are given in figures 6.1 and 6.2 respectively.

Figure 6.1 Figure 6.2

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(ii) The diagrammatic representation of the constituent particles (atoms, ions, or molecules) present in a
crystal in a regular three-dimensional arrangement is called crystal lattice.
A unit cell is the smallest three-dimensional portion of a crystal lattice. When repeated again and again in
different directions, it generates the entire crystal lattice.
(iii) A void surrounded by 4 spheres is called a tetrahedral void and a void surrounded by 6 spheres is
called an octahedral void. Figure 1 represents a tetrahedral void and figure 2 represents an octahedral
void.

Figure 1 Figure 2

Question 1.8:
How many lattice points are there in one unit cell of each of the following lattice?
(i) Face-centred cubic
(ii) Face-centred tetragonal
(iii) Body-centred
 Answer
(i) There are 14 (8 from the corners + 6 from the faces) lattice points in face-centred cubic.
(ii) There are 14 (8 from the corners + 6 from the faces) lattice points in face-centred tetragonal.
(iii) There are 9 (1 from the centre + 8 from the corners) lattice points in body-centred cubic.

Question 1.9:
Explain
(i) The basis of similarities and differences between metallic and ionic crystals.
(ii) Ionic solids are hard and brittle.
 Answer
(i) The basis of similarities between metallic and ionic crystals is that both these crystal types are held by the
electrostatic force of attraction. In metallic crystals, the electrostatic force acts between the positive ions and the
electrons. In ionic crystals, it acts between the oppositely-charged ions. Hence, both have high melting points.
The basis of differences between metallic and ionic crystals is that in metallic crystals, the electrons are free to move
and so, metallic crystals can conduct electricity. However, in ionic crystals, the ions are not free to move. As a result,
they cannot conduct electricity. However, in molten state or in aqueous solution, they do conduct electricity.
(ii) The constituent particles of ionic crystals are ions. These ions are held together in three-dimensional arrangements
by the electrostatic force of attraction. Since the electrostatic force of attraction is very strong, the charged ions are
held in fixed positions. This is the reason why ionic crystals are hard and brittle.

Question 1.10:
Calculate the efficiency of packing in case of a metal crystal for
(i) simple cubic
(ii) body-centred cubic
(iii) face-centred cubic (with the assumptions that atoms are touching each other).
 Answer
(i) 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.
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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 one particle

Hence, packing efficiency

(ii) 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.
Let the radius of the atom be r.
Length of the body diagonal, c = 4r

From ΔFED, we have

From ΔAFD, we have

or,

Volume of the cube,

A body-centred cubic lattice contains 2 spheres.

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So, volume occupied by two spheres in the unit cell

(iii) 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 spheres per unit cell is 4.

So, volume occupied by four spheres in the unit cell

= 74%
 Thus, ccp and hcp structures have maximum packing efficiency.

Question 1.11:
Silver crystallises in fcc lattice. If edge length of the cell is 4.07 × 10−8 cm and density is 10.5 g cm−3,
calculate the atomic mass of silver.
 Answer
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It is given that the edge length, a = 4.077 × 10−8 cm

Density, d = 10.5 g cm−3
As the lattice is fcc type, the number of atoms per unit cell, z = 4
We also know that, NA = 6.022 × 1023 mol−1
Using the relation:

= 107.13 gmol−1
Therefore, atomic mass of silver = 107.13 u

Question 1.12:
A cubic solid is made of two elements P and Q. Atoms of Q are at the corners of the cube and P at the body-centre.
What is the formula of the compound? What are the coordination numbers of P and Q?
 Answer
It is given that the atoms of Q are present at the corners of the cube.

Therefore, number of atoms of Q in one unit cell

It is also given that the atoms of P are present at the body-centre.
Therefore, number of atoms of P in one unit cell = 1
This means that the ratio of the number of P atoms to the number of Q atoms, P:Q = 1:1
Hence, the formula of the compound is PQ.
The coordination number of both P and Q is 8.

Question 1.13:
Niobium crystallises in body-centred cubic structure. If density is 8.55 g cm−3, calculate atomic radius of
niobium using its atomic mass 93 u.
 Answer
It is given that the density of niobium, d = 8.55 g cm−3
Atomic mass, M = 93 gmol−1
As the lattice is bcc type, the number of atoms per unit cell, z = 2
We also know that, NA = 6.022 × 1023 mol−1
Applying the relation:

= 3.612 × 10−23 cm3

So, a = 3.306 × 10−8 cm
For body-centred cubic unit cell:

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= 1.432 × 10−8 cm
= 14.32 × 10−9 cm
= 14.32 nm

Question 1.14:
If the radius of the octachedral void is r and radius of the atoms in close packing is R, derive relation between r and R.
 Answer

A sphere with centre O, is fitted into the octahedral void as shown in the above figure. It can be observed from the
figure that ΔPOQ is right-angled
∠POQ = 900
Now, applying Pythagoras theorem, we can write:

Question 1.15:
Copper crystallises into a fcc lattice with edge length 3.61 × 10−8 cm. Show that the calculated density is
in agreement with its measured value of 8.92 g cm−3.
 Answer
Edge length, a = 3.61 × 10−8 cm
As the lattice is fcc type, the number of atoms per unit cell, z = 4
Atomic mass, M = 63.5 g mol−1
We also know that, NA = 6.022 × 1023 mol−1
Applying the relation:

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= 8.97 g cm−3
The measured value of density is given as 8.92 g cm−3. Hence, the calculated density 8.97 g cm−3 is in
agreement with its measured value.

Question 1.16:
Analysis shows that nickel oxide has the formula Ni0.98O1.00. What fractions of nickel exist as Ni2+ and Ni3+ ions?
 Answer
The formula of nickel oxide is Ni0.98O1.00.
Therefore, the ratio of the number of Ni atoms to the number of O atoms,
Ni : O = 0.98 : 1.00 = 98 : 100
Now, total charge on 100 O2− ions = 100 × (−2)
= −200
Let the number of Ni2+ ions be x.
So, the number of Ni3+ ions is 98 − x.
Now, total charge on Ni2+ ions = x(+2)
= +2x
And, total charge on Ni3+ ions = (98 − x)(+3)
= 294 − 3x
Since, the compound is neutral, we can write:
2x + (294 − 3x) + (−200) = 0
⇒ −x + 94 = 0
⇒ x = 94
Therefore, number of Ni2+ ions = 94
And, number of Ni3+ ions = 98 − 94 = 4

Hence, fraction of nickel that exists as Ni2+

= 0.959

And, fraction of nickel that exists as

= 0.041
Alternatively, fraction of nickel that exists as Ni3+ = 1 − 0.959
= 0.041

Question 1.17:
What is a semiconductor? Describe the two main types of semiconductors and contrast their conduction
mechanism.
 Answer
Semiconductors are substances having conductance in the intermediate range of 10-6 to 104 ohm−1m−1.
The two main types of semiconductors are:
(i) n-type semiconductor
(ii) p-type semiconductor
n-type semiconductor: The semiconductor whose increased conductivity is a result of negatively-
charged electrons is called an n-type semiconductor. When the crystal of a group 14 element such as Si or
Ge is doped with a group 15 element such as P or As, an n-type semiconductor is generated.
Si and Ge have four valence electrons each. In their crystals, each atom forms four covalent bonds. On the
other hand, P and As contain five valence electrons each. When Si or Ge is doped with P or As, the latter
occupies some of the lattice sites in the crystal. Four out of five electrons are used in the formation of four
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covalent bonds with four neighbouring Si or Ge atoms. The remaining fifth electron becomes delocalised
and increases the conductivity of the doped Si or Ge.

p-type semiconductor: The semiconductor whose increased in conductivity is a result of electron hole is
called a p-type semiconductor. When a crystal of group 14 elements such as Si or Ge is doped with a
group 13 element such as B, Al, or Ga (which contains only three valence electrons), a p-type of
semiconductor is generated.
When a crystal of Si is doped with B, the three electrons of B are used in the formation of three covalent
bonds and an electron hole is created. An electron from the neighbouring atom can come and fill this
electron hole, but in doing so, it would leave an electron hole at its original position. The process appears
as if the electron hole has moved in the direction opposite to that of the electron that filled it. Therefore,
when an electric field is applied, electrons will move toward the positively-charged plate through electron
holes. However, it will appear as if the electron holes are positively-charged and are moving toward the
negatively- charged plate.

Question 1.18:
Non-stoichiometric cuprous oxide, Cu2O can be prepared in laboratory. In this oxide, copper to oxygen ratio is slightly
less than 2:1. Can you account for the fact that this substance is a p-type semiconductor?
 Answer
In the cuprous oxide (Cu2O) prepared in the laboratory, copper to oxygen ratio is slightly less than 2:1. This means
that the number of Cu+ ions is slightly less than twice the number of O2− ions. This is because some Cu+ ions have
been replaced by Cu2+ ions. Every Cu2+ ion replaces two Cu+ ions, thereby creating holes. As a result, the substance
conducts electricity with the help of these positive holes. Hence, the substance is a p-type semiconductor.

Question 1.19:
Ferric oxide crystallises in a hexagonal close-packed array of oxide ions with two out of every three
octahedral holes occupied by ferric ions. Derive the formula of the ferric oxide.
 Answer
Let the number of oxide (O2−) ions be x.
So, number of octahedral voids = x
It is given that two out of every three octahedral holes are occupied by ferric ions.

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So, number of ferric (Fe3+) ions

Therefore, ratio of the number of Fe3+ ions to the number of O2− ions,

Fe3+ : O2−

=2:3
Hence, the formula of the ferric oxide is Fe2O3.

Question 1.20:
Classify each of the following as being either a p-type or an n-type semiconductor:
(i) Ge doped with In (ii) B doped with Si.
 Answer
(i) Ge (a group 14 element) is doped with In (a group 13 element). Therefore, a hole will be created and the
semiconductor generated will be a p-type semiconductor.
(ii) B (a group 13 element) is doped with Si (a group 14 element). So, there will be an extra electron and the
semiconductor generated will be an n-type semiconductor.

Question 1.21:
Gold (atomic radius = 0.144 nm) crystallises in a face-centred unit cell. What is the length of a side of the cell?
 Answer
For a face-centred unit cell:

It is given that the atomic radius, r = 0.144 nm

So,
= 0.407 nm
Hence, length of a side of the cell = 0.407 nm

Question 1.22:
In terms of band theory, what is the difference
(i) Between a conductor and an insulator
(ii) Between a conductor and a semiconductor
 Answer (i) The valence band of a conductor is partially-filled or it overlaps with a higher energy,
 unoccupied conduction band.
 On the other hand, in the case of an insulator, the valence band is fully- filled and there is a
 large gap between the valence band and the conduction band.
(ii) In the case of a conductor, the valence band is partially-filled or it overlaps with a higher energy,
unoccupied conduction band. So, the electrons can flow easily under an applied electric field.

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On the other hand, the valence band of a semiconductor is filled and there is a small gap between the
valence band and the next higher conduction band. Therefore, some electrons can jump from the valence
band to the conduction band and conduct electricity.

Question 1.23:
Explain the following terms with suitable examples:
(i) Schottky defect (ii) Frenkel defect (iii) Interstitials and (iv) F-centres
 Answer
(i) Schottky defect: Schottky defect is basically a vacancy defect shown by ionic solids. In this defect, an
equal number of cations and anions are missing to maintain electrical neutrality. It decreases the density
of a substance. Significant number of Schottky defects is present in ionic solids. For example, in NaCl,
there are approximately 106 Schottky pairs per cm3 at room temperature. Ionic substances containing
similar-sized cations and anions show this type of defect. For example: NaCl, KCl, CsCl, AgBr, etc.

(ii) Frenkel defect: Ionic solids containing large differences in the sizes of ions show this type of defect.
When the smaller ion (usually cation) is dislocated from its normal site to an interstitial site, Frenkel
defect is created. It creates a vacancy defect as well as an interstitial defect. Frenkel defect is also known
as dislocation defect. Ionic solids such as AgCl, AgBr, AgI, and ZnS show this type of defect.

(iii) Interstitials: 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.

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(iv) F-centres: When the anionic sites of a crystal are occupied by unpaired electrons, the ionic sites are
called F-centres. These unpaired electrons impart colour to the crystals. For example, 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.

Question 1.24:
Aluminium crystallises in a cubic close-packed structure. Its metallic radius is 125 pm.
(i) What is the length of the side of the unit cell?
(ii) How many unit cells are there in 1.00 cm3 of aluminium?
 Answer
(i) For cubic close-packed structure:

= 353.55 pm
= 354 pm (approximately)
(ii) Volume of one unit cell = (354 pm)3
= 4.4 × 107 pm3
= 4.4 × 107 × 10−30 cm3
= 4.4 × 10−23 cm3

Therefore, number of unit cells in 1.00 cm3 =

= 2.27 × 1022

Question 1.25:
If NaCl is doped with 10−3 mol % of SrCl2, what is the concentration of cation vacancies?
 Answer
It is given that NaCl is doped with 10−3 mol% of SrCl2.
This means that 100 mol of NaCl is doped with 10−3 mol of SrCl2.

Therefore, 1 mol of NaCl is doped with mol of SrCl2

= 10−5 mol of SrCl2
Cation vacancies produced by one Sr2+ ion = 1

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Hence, the concentration of cation vacancies created by SrCl2 is 6.022 × 108 per mol of NaCl.

Question 1.26:
Explain the following with suitable examples:
(i) Ferromagnetism (ii)Paramagnetism (iii)Ferrimagnetism (iv)Antiferromagnetism
(v)12-16 and 13-15 group compounds.
 Answer
(i) 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 and 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

(ii) 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.
(iii) 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

(iv) Antiferromagnetism: 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 antiferromagnetic substances

(v) 12-16 and 13-15 group compounds: The 12-16 group compounds are prepared by combining group 12 and group
16 elements and the 13-15 group compounds are prepared by combining group 13 and group15 elements. These
compounds are prepared to stimulate average valence of four as in Ge or Si. Indium (III) antimonide (IrSb), aluminium
phosphide (AlP), and gallium arsenide (GaAS) are typical compounds of groups 13-15. GaAs semiconductors have a
very fast response time and have revolutionised the designing of semiconductor devices. Examples of group 12-16
compounds include zinc sulphide (ZnS), cadmium sulphide (CdS), cadmium selenide (CdSe), and mercury (II)
telluride (HgTe). The bonds in these compounds are not perfectly covalent. The ionic character of the bonds depends
on the electronegativities of the two elements.

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