Solid States

General Properties
y Solid is that state of a matter in which Concept Ladder
constituents are firmly bound because of
strong forces. Matter can exist in one of
y They have definite mass, shape and volume. three main states : solid,
y They are incompressible, rigid and have liquid, or gas.
strength. Three phases of water
y They have close packed arrangement of Ice (solid), Water (liquid)
particles. and Steam (gas)
y They have high density but very slow
diffusion rate.
y They can only have vibrational motion as
constituents have fixed positions.

Types of Solids
Solids are classified into 2 types, crystalline
and amorphous. Rack your Brain

Crystalline Solids Why density of ice is lower than

y In crystalline solids, constituents are arranged water?
in a definite or proper order which repeats
itself over long distances.
y They generally have definite geometry having
flat faces and sharp edges.
y They have sharp melting points.
y They are considered true solids.
y They give clean cleavage with fixed cleavage
planes. Concept Ladder
y They show anisotropic behaviour which means
different physical properties in different Isotropic : Properties of a
material are identical in all
directions because of orderly arrangement of
directions.
constituents.
Anisotropic : Properties
y They are incompressible. For example, CaF2,
of a material depend on
ZnS, diamond, quartz, NaX.
the direction; for example,
y All elements and compounds are of this type.
wood. In a piece of wood,
you can see lines going in
Amorphous Solids
one direction; this reaction
y In these type of solids, constituents are not
is referred to as “with the
arranged in a regular or orderly manner for
Solid States

grain”.
long range.

1.
 y They do not have sharp melting points.
y They are pseudo solids. Concept Ladder
y They show isotropic behaviour which is same
as physical properties in all directions because There exists strong
of irregular arrangement. electrostatic force in ionic
y They do not give clean cleavage. They have crystalline solids like NaCl
irregular cut. because of attraction
E.g., glass, plastic, and rubber between anions and
cations.
Terms related to crystalline solids
Crystal: This is a homogeneous part of solid
substance which is made by regular pattern
of structural units which are bonded by plane
surface making definite angles with each other.

Crystal lattice or space lattice: It is regular

arrangement of constituent particles (atom, ions
etc.) of a crystal in 3-D space.
Face: It is plane surface of crystal. Rack your Brain
Edge: It is formed because of intersection of two
adjacent faces. What is interfacial angle between
two adjacent faces of a cube?
Interfacial angle: It is angle between
perpendiculars of two intersecting faces.

Q.1 Why is glass of window panes of very old buildings found to be thicker at the
bottom than at the top and why is it milky?

A.1 Glass is amorphous solid which is a supercooled liquid of high viscosity and
hence possesses fluidity. Due to presence of this property it is thicker at the
bottom than at the top. Milkiness of glass is due to fact that it undergoes
heating during the day and cooling at night, i.e., annealing over several years.
as a result, it acquires some crystalline character..

Types of crystalline solids

Nature of constituent particles and binding
forces of crystalline solids are generally classified
as shown in table given below.
Solid States

2.
Types of Crystalline Solids

Solid angle When three or more than three edges are intersect, a solid angle is formed.

Bragg’s Equation
Max von Laue identified possibility of
diffraction of X-rays by crystals as order of
wavelength of X-rays is compatible to inter-
atomic distances present in a crystal.
y Bragg’s equation gives a simple relationship
between wavelength of X-rays and distance
Concept Ladder
between planes in crystal and angle of
reflection. The equation can be given as:
Due to their bonding,
nλ = 2d sin θ metallic solids have
Here, delocalised electrons.
λ = Wavelength of X-rays These free electrons can
n = Order of reflection it is taken generally move around, therefore
as 1. they can conduct
θ = Angle of incident light electricity. But in ionic
d = Distance between 2 layers of crystals solids electrons are not
free to move so they can’t
Solid States

conduct electricity.

3.
 y For a given number of lattice planes, value of
‘d’ is fixed so possibility of getting maximum
reflection depends only on q. If we increase q
gradually several positions will be observed
at which there will be maximum reflection.

Applications
y Bragg’s observation has proved to be highly
useful in determination of structures and
dimensions of ionic crystalline solids.
y It also explains many properties of X-rays. Rack your Brain
y Equation helped in construction of an X-ray
spectrometer to describe crystalline structure What is the shape of unit cell iof
of crystals as in case of face-centered cubic NaCl crystalline structure?
structure of NaCl.

Unit Cell
y Unit cell is the smallest unit or three-
dimensional portion of the space lattice
which when repeated and again in different
directions gives rise to the complete space
lattice.
y It has characteristics properties of a, b, c Previous Year’s Questions
(edge distance) and a, b, g, (angles).
y It is smallest geometrical figure which has The number of carbon atoms per
properties of a crystal in a lattice. unit cell of diamond is
y A crystal can have infinite number of unit [NEET-2013]
cells. (1) 6 (2) 1
Solid States

(3) 4 (4) 8

4.
Types of Unit Cell
They are of four types, namely, simple, face-
centred, end-centred and body-centred.
Simple or primitive or basic unit cell: In this,
lattice points (particles) are present only at Concept Ladder
corners.
Face-centred unit cell: In this, lattice points or In cube of any crystal
particles are present not only at corners but also A-atom placed at every
at centre of each face. corners and B-atom placed
Body-centred unit cell: In this, particles are at every centre of face. The
present at all the corners and body centre of unit formula of this compound
cell. is AB3.
End-centred unit cell: In this, particles are
present at all the corners as well as at centre of
2 opposite faces .

Types of Symmetry in Crystals

A crystal can have centre of symmetry, axis of

symmetry and plane of symmetry. Rack your Brain
y Plane of symmetry (POS): It is an imaginary
plane which passes from centre of crystal What is the symmetry of PCl5
and divides it into two equal part. (mirror molecule?
images of each other).
y Centre of symmetry: It is an imaginary point
which separates surface of crystal which is
at equal distances in both the directions by
Solid States

drawing any line through it.

5.
 y A crystal generally has one centre of symmetry.
y Axis of symmetry is imaginary straight line Concept Ladder
which on rotation of crystal gives same
appearance more than a single time.
y It is 2-fold, 3- fold, 4-fold and 6-fold type A sphere has all kinds of
respectively. symmetry of point, axis
and plane.
Crystal Systems
There are 7 types of crystal systems and
fourteen bravais lattices as given in table below

Crystal Systems and Bravais Lattices

Solid States

6.
Symmetry in Crystals
(a) Rectangular Plane of Symmetry (b) Diagonal Plane of Symmetry

(c) Axis of Four Fold Symmetry (d) Centre of Symmetry

Mathematical Analysis of Cubic System

Atomic Radius (r)
Previous Year’s Questions
y Atomic radius: It is half the distance between
two nearest neighbour atoms in crystal. For orthorhombic system axial
y It’s expressed in terms of length of edge ratios are a ≠ b ≠ c and the axial
angles are
(a) Of unit cell of a crystal.
a [AIPMT]
y In simple cubic r = (1)       90
2
a (2)       90
y In face-centred cubic (FCC) r =
2 (3)     90,   90
3a (4)       90
y In body-centred cubic (BCC) r =
4
Solid States

7.
 No. of Atoms Per Unit Cell/ Unit Cell Content (Z)
y It is total number of atoms contained in a Concept Ladder
unit cell.
nc ne nf ni A point lying at the corner
Z= + + + of a unit cell is shared
8 4 2 1
equally by eight unit cells
Where; nc = no. of atoms at corner position and therefore, only one-
ne = no. of atoms at edge center eighth portion of each of
nf = no. of atoms at face center position such a point belongs to the
ni = no. of atoms present at the center given unit cell.

1
y In SCC, Z = 8 × =1
8
Every corner atom is shared by surrounding
1 Rack your Brain
unit cells so it accounts for of an atom.
8
y In a FCC structure, Z = 3 + 1 = 4 Find out the two nearest atoms
1 in FCC and BCC crystalline
Eight(8) corner atoms contribute of an
8 structures and also find their
atom. radii?
which means only of one atom per unit cell.
Each of 6 face-centred atoms are shared by
two adjacent unit cells such that only half of
one face- centred atom is contributed as its
share that is, Previous Year’s Questions

1
6× 3 (atoms per unit cell)
= The number of atoms in 100 g of a
2
fcc crystal with density d = 10 g/
total of 4 atoms per unit cell. cm3 and cell edge equal to 100 pm,
y In a BCC structure, Z = 1 + 1 = 2. Each of eight is equal to
corner atoms will be contributing only 1 atom [AIPMT]
per unit cell. (1) 2 × 10
25
(2) 1 × 1025

Central atom has contribution of only one (3) 4 × 10

25
(4) 3 × 1025
atom per unit cell.
Solid States

8.
Coordination Number (C. No.)
y It is equal to the number of nearest neighbours
atom, that is, touching particles present
around a species in a crystal. Its larger value
Concept Ladder
shows closer packing.
y The values depend upon structure of crystal.
In ionic crystal, the number
S.C : Coordination number is 6 of oppositely charged
FCC : Coordination number is 12 ions surrounding each
BCC : Coordination number is 8 ion is known to be its
coordination.
NaCl ; CsCl ; ZnS ; CaF4 ; Na2O
6:6 8:8 4:4 8:4 4:8

Density of Lattice Matter (d)

y Density of lattice matter is ratio of mass per
unit cell to total volume of unit
cell and it is given as:
Z × Atomic weight
d= Previous Year’s Questions
N0 × Volume of unit cell (a3 )
Here, A metal crystallises with a face
N0 = Avogadro number centred cubic lattice. The edge
a3 = Volume of the unit cell is 408 pm. The
Z = Number of atoms in unit cell diameter of the metal atom is
a = Edge length in cm [AIPMT-2012]
d = Density in g/ml or g/cm3 (1) 288 pm (2) 408 pm
(3) 144 pm (4) 204 pm
Solid States

9.
 Packing Fraction
y ⚫ It is defined as the ratio of volume Concept Ladder
4 
occupied by spheres  r 3  in a unit cell to
3  A crystal may have a
the total volume (a3) of that unit cell. Fraction nubmer of planes or
of volume that is empty is called void fraction. axis of symmetry but it
4 3 possesses only one centre
Z× πr of symmetry.
P.F. = 3
a3
y In a SCC,
4 3
πr
P.F.
= 3= 0.52
= 52%
(2r)3

Rack your Brain

Why the closest packed

structures have high value of
coordination?

Here, a = 2r; % void = 48%

y In a body-centred cubic structure,

4 3
2r
P.F.  3  0.68  68%
3
 4r 
  Previous Year’s Questions
 2
The intermetallic compound LiAg
crystallizes in cubic lattice in
which both lithium and silver have
coordination number of eight. The
crystal class is
[AIPMT]
(1) face-centred cube
(2) simple cube
4r
Here, a = ; % void = 32% (3) body-centred cube
Solid States

3 (4) none of these

10.
y In a face-centred cubic structure,

Concept Ladder

y In fcc, the nearest

neighbour of a corner
atom is the face centred
atom and thus, atom
on each corner has 4
4 3 nearest neighbours.
4× πr y It also possesses four
P.F.
= 3= 0.74
= 74%
 4r 
3
face centred atoms
  in planes below and
 2
3 above it.
 4r 
Here, a =  
 2
% void = 26%

Solid States

11.
 Interstitial Voids
Interstitial voids are spaces left after hexagonal Concept Ladder
close packing (hcp) and cubic close packing (ccp).
The spaces or voids are of the following types:
Voids are terms as
Trigonal void: It is a vacant space touching three the gaps between the
spheres that is, two-dimensional void formed constituent particles in a
when three spheres are in same plane having closed packed structure.
corners are at corners of triangle. Close packing in solids can
be generally done in three
Tetrahedral voids: Vacant space created when ways : 1D close packing, 2D
each sphere of second layer rests on vacant close pakcing and 3D close
space created by three spheres (of first layer) packing.
touching each other is called a tetrahedral void.

Octahedral voids: They are formed by combination

of two triangular voids of first and second layers.
They are so called because they are enclosed
between six spheres, centres of which occupy
corners of a regular octahedron.

Location and number of voids Rack your Brain

(1) Tetrahedral void: They are located at body
diagonals, two in each body diagonal at one What is the coordination number
fourth of the distance from each end. for tetrahedral void?
Number of Tetrahedral voids = 8

(2) Octahedral voids: These are located at middle

of cell edges and at centre of cubic unit cell.
1
Total number of Octahedral voids = × 12 + 1 = 4
4
Size of voids:
Voct = 0.414 × r Previous Year’s Question
Vtetra = 0.214 × r
The number of octahedral void(s)
Vtri = 0.115 × r per atom present in a cubic close-
packed structure is
where r is radius of the biggest sphere.
[AIPMT-2012]
(1) 1 (2) 3
Solid States

(3) 2 (4) 4

12.
Radius Ratio
Radius ratio is radius of octahedral void Concept Ladder
to radius of sphere forming close packed
arrangement.
The packing density data
(1) For stability of ionic compounds, each cation reveals that close packing
must be surrounded by maximum no, of anions of atoms in cubic structure
and vice-versa. follow the order, FCC > BCC
> SCC, i.e., more closely
(2) The maximum no. of opposite charged ions packed atoms are in FCC
surrounding another ion is known as coordination structure.
number. Since, ionic bonds are non- directional
arrangement of ions in crystal is determined by
sizes.

Ratio of radius of cation to anion is known as

radius ratio, i.e.,

Radius of the cation(r + )

Radius Ratio = Rack your Brain
Radius of the anion(r − )
If the radius of the bromide ion
(4) If radius ratio is greater, then size of cation
is 0.182 nm, how large a cation
is larger and therefore greater is its coordination
can fit in each of the tetrahedral
number.
hole?
(5) Relationships between radius ratio and the
coordination number and structural arrangement
are called radius ratio rules.

Q.2 The two ions A+ and B- have radii 88 and 200 pm respectively. In the close
packed crystal of compound AB, predict the coordination nubmer of A+.

A.2 r r(A  )
 
88 pm
 0.44
r r(B ) 200 pm


It lies in the rage 0.414 to 0.732

Hence, the coordination number of A+ = 6
Solid States

13.
 Packing of Constituents in Crystals
Crystal constituents can be packed in two
dimensions and 3-Dimensions.

Close Packing in Two Dimensions

In this, close packing arrangement
in two dimensions are as follows:
Previous Year’s Questions
Square close packing
y In this, each sphere is in contact with four In crystals of which one of following
other spheres. ionic compounds would you expect
y Voids form a square in this type of packing. maximum distance between
y About 52.4% space is occupied by the spheres. centres of cations and anions?
[AIPMT]
(1) CsI (2) CsF
(3) LiF (4) LiI

Q.3 The edge length of a unit cell of a metal having molecular mass 75 g/mol is 5Å
which crystallizes in a cubic lattice. If the density is 2 g/cc, then find the radius
of the metal atom.

A.3 
Z M
a 3  N0
  a 3  N0 2  (5  108 )3  6.02  1023
or Z   2
M 75
This shows that the metal has body-centred cubic lattice.
For BCC lattice,

3 1.732
r a  5Å  2.165Å
4 4
Solid States

14.
Hexagonal close packing
y It is more densely packed than square closed
Concept Ladder
packing.
y In this, voids are triangular.
y In this, 60.4% space is occupied by spheres. In 2D hexagonal close
pakcing, their is less free
space between sphere
than 2D square close
packing. Thus hexagonal
close pakcing is denser
than square close packing.

Rack your Brain

At what angle the HCP structure

can be rotated so that it appears
same as original one?

Packing in Three Dimensions

This packing is of following three types:
Previous Year’s Questions
Hexagonal close packing
y Atoms are present at center and at corners of A compound is formed by cation
two hexagons placed parallel to each other, C and anion A. The anoins form
3 more atoms are placed in a parallel plane hexagnoal close packed (hcp)
midway between the two planes. lattice and the cations occupy 75%
y It generally has a six-fold axis of symmetry. of octahedral voids. The formula of
y In this, packing gives an arrangement of the compound is
layers as AB AB, that is, odd number layers [NEET-2019]
are similar and so are even number layers. (1) C4A3 (2) C2A3
Solid States

(3) C3A2 (4) C3A4

15.
 Concept Ladder

In both hexagonal close

packing (hcp) and cubic
close packing (ccp) the
coordination number of
Cubic close packing spheres remian twelve.
y Sphere in fourth layer will correspond to that
in first layer and give rise to ABC, ABC, type
of packing.
y It has 3-fold axis of symmetry which pass
through the diagonal of the cube.
y Here coordination number is 12. Examples:
Cu, Ag, Au, Ni, Pt

Previous Year’s Questions

Structure of a mixed oxide is cubic

close packed (ccp). The cubic unit
cell of mixed oxide is composed
of oxide ions. One fourth of the
tetrahedral voids are occupied by
divalent metal A and the octahedral
voids are occupied by a monovalent
metal B. The formula of the oxide is
[AIPMT-2012]
(1) ABO2 (2) A2BO2
(3) A2B3O4 (4) AB2O2
Solid States

16.
17.
Solid States
 Body-centred cubic packing
y In this, each sphere is in contact with 8 Concept Ladder
spheres: 4 in lower layer and four in upper
layer.
y Ionic solids have
y It is possible when spheres in first layer are
consituents particles
slightly opened that is none of spheres is
as ions. These are
touching the other. Examples: Li, Na, K, Rb,
formed by arrangement
Cs, Ba
of cations and anions
by strong Coulombic
Structure of Some Ionic Solids
forces and also are hard
Rock salt (NaCl) type
and brittle in nature.
y Cl– has a close cubic packing (ccp) type
y Ionic solids acts as an
structure that is face centred cubic type (fcc).
insulator in its solid
y In this, Na+ occupies octahedral spaces.
states where as they
y Na+ and Cl– have coordination number 6.
acts as conductors in
y No. of formula units per unit cell are 4.
r + its molten and aqueous
y Theoretically, Na should be 0.414 but it is states.
rCl −
0.525. Examples: LiX, NaX, KX, AgCl, AgBr,
NH4Cl.

CsCl type
y In this, Cl– ions are at corners of cube and Cs+
ions are in cubic void.
y Coordination number of both Cs+ and Cl– is 8.
y In this, number of formula units per unit cell
is 1.
r + Rack your Brain
y Theoretically, Cs should be 0.732 but it is 0.93.
rCl −
In NaCl type structure, the larger
Examples: CsX, TiCl, TiBr, NH4Cl, NH4Br
atoms form _______ arrangement
and smaller atoms fill all ______
Zinc Blend (ZnS type)
voids.
y In this, S2– occupies CCP while Zn2+ ions occupy
alternate tetrahedral voids.
y Only half of total voids are occupied.
y In this, coordination no.of both Zn2+ and S2– is
4.
y No. of formula units in a unit cell is 4.
Examples: ZnS, CuCl, CuBr, CuI, AgI, BeO
Solid States

18.
Fluorite structure (CaF2 type)
y In this, Ca2+ occupies CCP and F– occupies all Concept Ladder
tetrahedral voids.
y Also, coordination no. of Ca2+ is 8 while for
F– it is 4. The crystal in which all the
y In this, no. of formula units per unit cell is lattice points are occupied
Examples: CaF2, BaCl2, BaF2, SrF2. by the component particles
or groups of particles is
Antifluorite structure (Na2O type) knonw as ideal crystal.
y Here negative ions (O2–) occupy ccp while With change in
cations (Na+) occupy all the tetrahedral voids. temperature, molecular
y Co-ordination no. of Na+ is 4 while for O2– . motion increases, which
It is 8. causes deviation from
y In this, no. of formula units per unit cell is 4. ordered arrangement and
Examples: Na2O, Li2O, K2O. gives rise to a defect or
imperfection in the crystal.
Normal spinel structure (AB2O4)
They have a general formula AB2O4.
A Bivalent Cation (Mg+2)
B Trivalent Cation (Al3+)
y MgAl2O4 is spinel crystal.
y In this, Mg2+ occupy tetrahedral voids while Rack your Brain
oxide ions occupy CCP. Aluminium occupies
octahedral voids.
Coordination number of fluorine
y Ferrites [ZnFe2O4] can also have structure.
in calcium chloride is?
y They are used in telephones, memory loops of
computers as magnetic material.

Structure of Fe3O4 (Magnetite)

y In Fe3O4, Fe3+ and Fe2+, they are present in 2:1
ratio.
y In this, oxide ions are in CCP. Fe2+ occupies Previous Year’s Questions
octahedral voids where as Fe3+ occupies
octahedral and tetrahedral voids.
Formula of nickel oxide with metal
y MgFe2O4 also has this kind of structure
deficiency defect in its crystal is
Ni0.98O. The crystal contains Ni2+
Imperfections In Solids
and Ni3+ ions. The fraction of nickel
y Deviation from perfectly ordered arrangement
existing as Ni2+ ions in the crystal is
constitutes a defect or imperfection.
[NEET-2019]
y The defects are also called thermodynamic
Solid States

(1) 0.96 (2) 0.04

defects as a number of the defects depend
(3) 0.50 (4) 0.30
on temperature.

19.
 y Crystals may possess additional defects
because of presence of impurities.
Imperfection not only modifies properties of
solids but also gives rise to new properties.

Electronic Imperfection
Electrons are present in fully occupied lowest
energy states but at very high temperatures Previous Year’s Questions
few electrons may occupy higher energy states
depending upon the temperature. Which one of following elements
y For example, in crystals of pure silicon or silicon should be doped so as to
germanium some electrons are released give p-type of semiconductor?
thermally from covalent bonds at temperature
above 0 K. These electrons are free to move [AIPMT]
in crystal and are responsible for electrical (1) Selenium (2) Boron
conductivity. This type of conduction is called (3) Germanium (4) Arsenic
as intrinsic conduction.
y Electron deficient bond formed by release of
an electron is known as hole. In presence of
an electric field the positive holes move in
a direction opposite to that of the electrons
and conduct electrically.

Q.4 Why stoichiometric defects are also called intrinsic defects?

A.4 Stoichiometric defects are called because they do not change the stoichiome-
try of the crystal (Schottky defect and Frenkel defect). They are called intrinsic
defects because it is due to the deviation from regular arrangement of atoms
or ions within the crystal and no external substance is added..

Q.5 CaCl2 will introduce Schottky defect if added to AgCl crystal. Explain.

A.5 Two silver ions will be replaced by one calcium ions to maintain electrical neu-
trality. So, a hole is created at the lattice site for every Ca2+ ion introduced..
Solid States

20.
Atomic Imperfection
Compounds in which number of irregularities Concept Ladder
present in arrangement of atoms or ions are
called atomic imperfections. It is of two types:
In Schottky defect the
Stoichiometric defects: Compounds in which density of crystal decreases.
number of positive and negative ions are The crystal begins to
exactly in ratio indicated by the chemical formula conduct electricity to small
are known as stoichiometric compounds for extent by ionic mechanism.
example, NaCl.

These solids show following types of defects:

(a) Schottky defect: Schottky defect is created

when same number of negative and positive

ions are missing from respective positions

Rack your Brain
leaving behind a pair of holes.
Explain why ZnO becomes yellow
on heating.

Previous Year’s Questions

The correct statement regarding

y Schottky defect more common in ionic defects in crystalline solids is
compounds with high coordination number [NEET-2015]
and where size of negative and positive (1) Frenkel defects decrease the
ions is almost equal. density of crystalline solids
y This defect decreases density of crystals but (2) Frenkel defect is a dislocation
maintain neutrality e.g., NaCl, CsCl, KCl, KBr. defect
In case of NaCl, there is nearly 106 Schottky (3) Frenkel defect is found in
pairs per cm3 at room temperature. halides of alkaline metals
(4) Schottky defects have no effect
Solid States

on the density of crystalline solids.

21.
 (b) Interstitial defect: Interstitial defect is caused
due to the presence of ions in the normally Concept Ladder
vacant interstitial sites in the crystal.
Generally, cations are
(c) Frenkel defect: Frenkel defect is created smaller than anions, hence
when an ion leaves its correct lattice site and it is more common to find
occupies an interstitial site. This defect is the cations occupying the
interstitial sites.
common in ionic compounds which have low
coordination number and in which there is
large difference in size between negative and
positive ions. Due to this defect, neutrality
density remains same but dielectric constant
of the medium increases.

For example, ZnS, AgCl, AgBr, AgI etc.

Rack your Brain

State whether the density of

solid remains same or not for
Frenkel defect.

Previous Year’s Questions

Non-stoichiometric defect: In Non-stoichiometric
defect many compounds in which ratio of The appearance of colour in solid
positive and negative ions differs from what is alkali metal halides is generaly due
required by the ideal formula of the compound. to
[AIPMT]
Such compounds are called non-stoichiometric
(1) interstitial positions
compounds, for example, VOx . In this type of
(2) F-centres
compounds, a balance of positive and negative (3) Schottky defect
charges is always maintained by having extra (4) Frenkel defect
Solid States

electrons or extra positive charge.

22.
These defects are explained below:
(a) Metal excess defects due to anion vacancies Concept Ladder
y Compound may have excess metal ions if a
negative (–ve) ion is absent from its lattice Defects due to interstitial
site, leaving a hole which is engaged by an cations is shown by crystals
electron to maintain electrical neutrality. which are likely to exhibit
Frenkel defect. An excess
y Holes occupied by electrons are called
positive ion is located in
F-centres and are responsible for colour of the interstitial sites.
compounds, examples are,
1. Excess of Na in NaCl makes crystal appear
yellow.
2. Excess of Li in LiCl makes it pink.
3. Excess of K in KCl makes it violet.
y Greater the number of F-centres, greater will Rack your Brain
be intensity of colour. This kind of defect is
found in crystal which is likely to possess Write some difference between
Schottky defect. stiochiometric and non-
stiochiometric defects.

Previous Year’s Questions

Ionic solids, with Schottky defects,

contain in their structure
[AIPMT]
(1) cation vacancies only
(2) cation vacancies and interstitial
(b) Metal excess defects cations
y This defect occurs if an extra positive ion is (3) equal number of cation and
present in an interstitial site. anion vacancies
y Electrical neutrality is sustained by presence (4) anion vacancies and interstitial
of an extra electron in interstitial site. anions.
Solid States

23.
 y The type of defect is shown by crystals which
are likely to show Frenkel defects, for example, Concept Ladder
yellow colour of Zn.

When extra positive ions

occupy interstitial site
to maintain electrical
neutrality, some extra
electron occupy some
other interstitial sites.

(c) Metal deficiency due to cation vacancies

Rack your Brain
y Non-stoichiometric compounds can have
metal deficiency due to absence of a metal What will be the colour of KCl
ion from their lattice site. crystal mixed in the atmosphere
y The charge is balanced by an adjacent ion K?
having high positive charge.
y These type of defect is generally shown by
compounds of transition metals, for example,
FeO, FeS and NiO.

Previous Year’s Questions

If NaCl is doped with 10-4 mole % of

SrCl2. Calculate the concentration
of cation vacancies?
(NA = 6.02 × 1023 mol-1)
[AIPMT]
(1) 6.02 × 10 mol
16 -1

(2) 6.02 × 1017 mol-1

(3) 6.02 × 1014 mol-1
Solid States

(4) 6.02 × 1015 mol-1

24.
Magnetic Properties of Solids

Diamagnetic substances: Concept Ladder

They are weakly repelled by magnetic field
and do not have any unpaired electron, i.e., all The temperature at which
paired electrons. a feromagnetic substance
loses its ferromagnetism
and attains paramagnetism
only is known as Curie
temperature. For Iron the
For example, NaCl, Zn, Cd, Cu+ , TiO2. Curie temperature is 1033K
y They act as electrical insulators. and Ni it is 629K.

Paramagnetic substances:
They are attracted by magnetic field and
have unpaired electrons. They lose magnetism in
absence of magnetic field.

Rack your Brain

For example,
Mention some application based
1. Metal oxides like CuO, VO2 etc.
on ferromagnetic and anti-
2. Transition metals for example, Cr, Mn, Ni, Co,
ferromagnetic substances.
Fe etc.

Ferromagnetic substances:

They are attracted by magnetic field and

show permanent magnetism even in absence of
magnetic field. Some examples are, Fe, Co, Ni,
CrO2 (used in the audio and video tapes) Fe3O4
etc.
y Ferromagnetism arises because of Concept Ladder
spontaneous alignment of magnetic moments
in same direction. A material is diamagnetic
if it tends to move out
of a magnetic field and
paramagnetic if it tends to
Solid States

y When we go above curie point/curie move into a magnetic field.

temperature ferromagnetism doesn’t exist.

25.
 Anti-ferromagnetic substances:
They are expected to possess paramagnetism Concept Ladder
or ferromagnetism on basis of unpaired electrons
but in real have zero net magnetic moment, some Solids are classified
examples are, MnO, MnO2, Mn2O3, FeO, Fe2O3. into three groups
Anti-ferromagnetism occurs when number of viz – conductors,
parallel magnetic moments is equal to number semiconductors and
insulators. Conductivity of
of anti-parallel magnetic moments. This results
metal ranges from 10-7 – 104
in a net zero magnetic moment. ohm m, for semi conductor
from 10-6 – 104 ohm m and
for insulators from 10-10 –
10-20 ohm m.
Ferrimagnetic substances:
In case of ferrimagnetic substances, there
are unequal number of parallel and anti-parallel
magnetic moments which lead to net magnetic
Rack your Brain
moment, for example, Fe3O4, ferrites.

Name the process of introducing

an impurity into semi-conductors
to enhance their conductivity.
Ferrimagnetic, anti-ferromagnetic and
ferromagnetic solids change into paramagnetic
substance at a particular temperature. For
example, ferrimagnetic Fe3O4 on heating to 850
K becomes paramagnetic. This is because of Previous Year’s Questions
alignment of spins in one direction on heating.
If we mix a pentavalent impurity
Curie Temperature in a crystal lattice of germanium,
The ferromagnetic substance has a what type of semiconductor
formation will occur?
characteristic temperature above which no
[AIPMT]
ferromagnetism is seen. It is known as curie (1) n-type semiconductor
temperature. (2) p-type conductor
(3) Both (1) and (2)
(4) None of these
Solid States

26.
Electrical Properties of Solids
Piezoelectricity: It is electricity produced when
Concept Ladder
mechanical force is applied on polar crystals due
to displacement of ions. A piezoelectric crystal
acts like a mechanical electrical transducer. They y Diode is used as a
are used in record players. rectifier which is
formed by combinaiton
Pyroelectricity: It is the electricity produced of n-type and p-type
when some polar crystals are heated. e.g., LiNbO3. semiconductors.
Ferroelectricity: In few piezoelectric crystals, y Transistors can be ‘npn’
dipoles are permanently polarized even in or ‘pnp’ type which
absence of electric field. However, on applying are formed by making
electric field, direction of polarization changes. sandwitch of a layer of
The phenomenon is known as ferroelectricity p-type semiconductor
due to analogy with ferromagnetism. between two n-type
semiconductors (i.e.,
npn).

Barium titanate, sodium potassium tartrate

(Rochelle salt) and potassium dihydrogen
phosphate are some of polar crystals which
exhibit ferroelectricity.

Anti-ferroelectricity: In few crystals, dipoles

align in such a way that they alternately point
up and down in a manner that crystal does not
possess any net dipole moment, for example,
lead zirconate.

Previous Year’s Questions

On doping Ge metal with a little

Superconductivity: Superconductivity defined of In or Ga, one gets
when it offers no resistance to flow of electricity. [AIPMT]
(1) p-type semiconductor
There are no substances which are having super
(2) n-type semiconductor
conductance at room temperature.
(3) insulator
(4) rectifier
Solid States

27.
 y Superconductors: They are widely used in
building super magnets, electronic power
transmission, etc.
Examples: YBa2Cu3O7, Nb3 Ge alloy, La1.25
Ba0.15 CuO4 , (TMTSF)2 PF6 (TMTSF stands for Definition
tetra methyl tetra Selena fulvalene). The type of semiconductor
y Kammerlingh Onnes observed this formed by doping of impurities
phenomenon at 4K in mercury. to any substance is known as
Semiconductors: They are electronic conductors extensive semiconductors.
which have electrical conductivity in range of 104–
107 Ω–1 cms, for example, Sn, Ge, Si (grey only),
SiC, Cu2O.
y Pure substances which are semiconductors
which are known as intrinsic semiconductors,
for example, Si, Ge.
y In case of semiconductors, if conductivity is
due to impurities, they are known as extrinsic Rack your Brain
semiconductors.
y ⚫ Addition of impurities in to a semiconductor What are the group numbers
is known as doping. Example includes, when of elements which form
phosphorous and arsenic (5th group element) semiconducters substances?
are doped in silica (4th group element) n-type
of conductance is seen.
When a group 3rd element (for example, Ga)
is Doped, p-type of conductance is observed..

Q.6 Despite long-range order in the arrangement of particles why are the crystals
usually not perfect?

A.6 Crystallization process will be faster so that particle may not get enough time
to arrange in perfect order. That is why crystals have the long- range arrange-
ment of particles but not perfect..

Q.7 Why is FeO (s) not formed in stoichiometric composition?

A.7 The composition of Fe2+ and O2- ions is not 1:1 it is 0.95:1. This is obtained if
Solid States

and only if a small number of Fe2+ ions are replaced by two-third of Fe3+ in
OH sites..

28.
Q.8 Gold crystallizes in an FCC unit cell. What is the edge length of unit cell (r =
0.144 mm)?

A.8 r = 0.144 nm

a  2 2r
 2  1.414  0.144 nm
 0.407 nm

Q.9 Analysis shows that a metal oxide’s empirical formula is M0.98O1.00. Calcu late
the percentage of M2+ and M3+ ions in the crystal.

A.9 Let the M2+ ion in crystal be x

M3+ = 0.98 – x
Since, total charge on compound must be zero,
So, 2x + 3(0.98 – x) – z = 0
Or x  0.94
0.94
% of M2   100  97.9%
0.98
% of M3  100  97.9  2.1%

Q.10 Explain how electrical neutrality is maintained in compounds showing Frenkel

and Schottky defect.

A.10 The compound showing Frenkel defect, ions just get displaced within lattice,
while in compounds showing Schottky defect,have equal number of cations
and anions are removed from lattice. So it’s electrical neutrality is maintained
in both cases..

Q.11 The electrical conductivity of a metal decreases with rise in temperature while
that of a semi-conductor increases. Explain.

A.11 In metals with increase of temperature, kernels electrons start vibrating at

faster rate and thus offer resistance to own of electrons. Then conductivity of
metals decreases.
In case of semi-conductors (14th group elements), with increase of temper-
Solid States

ature, more electrons can shift from valence band to conduction band. Then
conductivity of semiconductors increases.

29.
 Q.12 What type of substances would make better permanent magnets –
ferromagnetic or ferromagnetic ? Why ?

A.12 Ferromagnetic substances make better permanent magnets. This is because

metal ions of a ferromagnetic substance are grouped into small regions known
as domains. Each domain acts as small magnet and get oriented in direction
of magnetic field in which it is placed. This persists even in absence of mag-
netic field.

Q.13 In a crystalline solid, the atoms A and B are arranged as follows :

(a) Atoms A are arranged in ccp array.
(b) Atoms B occupy all the octahedral voids and half of the tetrahedral voids.
What is the formula of the compound ?

A.13 No. of A (ccp) = 4

No. of B  octahedral voids 

Tetrahedral
2
8
4
2
8

A : B so, formula of the compound is AB2

4:8
1:2
AB2

Q.14 A unit cell consists of a cube in which X atoms are at the corners and Y atoms
are at the face centres. If two atoms are missing from two corners of the unit
cell, what is the formula of the compound?

A.14 Total contribution of ‘X’ atoms from 6 corners 

1
6 
3
8 4
Number of atoms of Y from face centres = 3
3
\x:y= : 3 = 3 : 12 or 1 : 4
4
Solid States

Hence, formula is XY4.

30.
Q.15 Calculate the number (n) of atoms contained within (a) simple cubic cell (b) a
body centred cubic cell (c) a face centred cubic cell.

A.15 (a) The simple cubic jnit cell has 8 atoms at eight corners. Each aotm is shared
by 8 unit cells.
1
 n  8  1
8
(b) The body centred cubic (BCC) cell consists of 8 atoms at the corners and
one atom at centre.
 1
 n  8    1  2
 8
(c) The face centred cubic (FCC) unit cell consists of 8 atoms at the eight
corners and one atom at all faces. This atom at the face is shared by two unit
cells.
1  1
 n  8   6    4
8  2

Q.16 Calculate number of atoms in a cubic unit cell having one atom on each corner
and tow atoms on each body diagonal.

A.16 There are total 4 body diagonals and there are 2 atoms at each body diagonal.
Hence nubmer of atoms from 4 diagonals = 8
Number of atoms from 8 corners = 1
\ Total number of atoms in this unit cell = 8 + 1 = 9

Q.17 In compound atoms of element Y forms ccp lattice and those of element X
occupy 2/3rd of tetrahedral voids. What is the formula of the compound ?
Solid States

31.
 A.17 No. of Y atoms per unit cell in ccp lattice = 4
No. of tetrahedral voids = 2 × 4 = 8
No. of tetrahedral voids occupied by X = 2/3 × 8 = 16/3
Therefore, Formula of the compound = X16/3Y4
= X16Y12
= X4Y3

Q.18 Potassium crystallizes in a body centred cubic lattice. How many unti cells are
present in 2g potassium? (At. mass of K = 39)

A.18 A bcc unit cell has 2 atoms per unit cell

2
\ Mole of potassium =
39
2  6.022  1023
Number of atoms of K 
39

Number of unit cells  2  6.022  10  1.54  1022

23

39  2

Q.19 A solid A+B- has NaCl type close packed structure. If the anion has a radius of
241.5 pm, what should be the ideal radius of the cation? Can a cation C+ having
radius of 50 pm be fitted into the tetrahedral hole of the crystal A+B-?

A.19 As A+B- has NaCl structure, A+ ions will be present in octahedral voids.
Ideal radius of cation will be equal to radius of the octahedral void becuase
in that case, it will touch the anions and arrangement will be close packed.
Hence,
Radius of octahedral void = rA+ = 0.414 × rB– = 0.141 × 241.5 pm = 100.0 pm
Radius of tetrahedral void = 0.225 × rB– = 0.225 × 241.5 pm = 54.3 pm
As radius of cation C+(50 pm) is smaller than size of tetrahedral void and can
be placed into tetrahedral voids (but not exactly fitted into it).
Solid States

32.
Summary

y In NaCl, there are nearly 106 Schottky pairs per cm3 at room temperature (As in 1
cm3 there are nearly 1022 ions so there is one schottky defect per 1016 ions.)
y Combination of ‘p’ and ‘n’ type semiconductors are used to make electronic
components e.g., Diode.
y On increasing temperature of CsCl structure the coordination number changes
from 8–8 to 6–6. While on increasing pressure in NaCl structure Co No increases
from 6–6 to 8–8.
y The production of frenkel or schottky defects is an endothermic process.
y He has HCP structure while rest of inert gases have C.C.P structure.
y The most unsymmetrical crystal system is Tri clinic as a ≠ b ≠ c and α ≠ β ≠ γ ≠ 90°.
y At the highest temperature at which super conductivity was called as 23 K in case
of alloys of Niobium.
y d–spacing: It is a distance between two parallel planes in a cubic lattice.
a
d=
h + k2 + l 2
2

Here, a = edge length

h, k, l = miller indices of plane.
y Atomic Radius → and Edge Length (a)

a
In a simple cubic unit cell r =
2

In face-centred cubic cell (FCC) r =

a
2
3a
In body-centred cubic cell (BCC) r =
4
y ⚫ No. of Atoms in a Unit Cell/ Unit Cell Content (Z)

nc nf ni
Z  
3 2 1
Here nc = 3, nf = 6 , ni = 1
Solid States

33.
 y Density of Lattice Matter (d)

Z × Atomic weight
d=
N0 × Volume of unit cell (a3 )
Here d = Density
Z = Number of atoms
N0 = Avogadro number
a3 = Volume
a = Edge length
y Packing Fraction

4 3
Z× πr
P.F = 3
a3
y Bragg’s Equation
nλ = 2d sinθ
Solid States

34.