12th CHEMISTRY

6.SOLID STATE
INTRODUCTION:
• Matter may exist in three different physical
states namely solid, liquid and gas.
• Solids differ from liquids and gases by
possessing definite volume and definite shape.
• In the solids the atoms or molecules or ion are
tightly held in an ordered arrangement and
there are many types of solids such as diamond,
metals, plastics etc., and most of the substances
that we use in our daily life are in the solid
state.
General characteristics of solids
• Unlike gases, in solids the atoms , ions or molecules are
held together by strong force of attraction.
• The general characteristics of solids are as follows,
(i) Solids have definite volume and shape.
(ii) Solids are rigid and incompressible
(iii) Solids have strong cohesive forces.
(iv) Solids have short inter atomic, ionic or molecular distances.
(v) Their constituents ( atoms , ions ormolecules) have fixed
positions and can only oscillate about their mean positions
Classification of solids:
Ionic crystals
(Ex: NaCl,KCl)

Covalent crystals
(Ex: Diamond, SiO2)

Molecular crystals
Crystalline
solids (Ex: naphthalene,
Classification of anthacene, glucose)

solids Metallic crystals

(All Metallic
Amorphous Elements(Na, Mg, Cu,
solids Au, Ag))
(Ex: NaCl, KCl)
Atomic solids(Ex:
Frozen Elements of
group 18 )
• We can classify solids into the following two major
types based on the arrangement of their constituents.
(i) Crystalline solids
(ii) Amorphous solids.
• The term crystal comes from the Greek word
“krystallos” which means clear ice.
• This term was first applied to the transparent quartz
stones, and then the name is used for solids bounded
by many flat, symmetrically arranged faces
• A crystalline solid is one in which its
constituents (atoms, ions or molecules), have an
orderly arrangement extending over a long
range.
• The arrangement of such constituents in a
crystalline solid is such that the potential energy
of the system is at minimum.
• In contrast, in amorphous solids (In Greek,
amorphous means no form) the constituents are
randomly arranged.
The following table shows the differences between crystalline and
amorphous solids
S. No Crystalline Solids Amorphous Solids
Long-range orderly arrangement of
1 Short-range, random arrangement of constituents.
constituents.
2 Definite shape. Irregular shape.
Generally crystalline solids are anisotropic
3 They are isotropic, like liquids.
in nature.

They are considered pseudo solids or supercooled

4 They are true solids.
liquids.
5 Definite heat of fusion. Heat of fusion is not definite.
Gradually soften over a range of temperature and can
6 They have sharp melting points.
be molded.
7 Examples: NaCl, diamond, etc. Examples: Rubber, plastics, glass, etc.
Isotropy The following figure illustrates the anisotropy in crystals
due to different arrangement of their constituents along
different directions
• Isotropy means uniformity in all
directions.
• In solid state isotropy means having
identical values of physical properties
such as refractive index, electrical
conductance etc., in all directions,
whereas anisotropy is the property
which depends on the direction of
measurement.
• Crystalline solids are anisotropic and
they show different values of physical
properties when measured along
different directions.
Classification of crystalline solids
Ionic solids:
• The structural units of an ionic crystal are
cations and anions. They are bound together by
strong electrostatic attractive forces.
• To maximize the attractive force, cations are
surrounded by as many anions as possible and
vice versa.
• Ionic crystals possess definite crystal structure;
many solids are cubic close packed.
• Example: The arrangement of Na+ and Cl- ions
in NaCl crystal.
Characteristics:
1. Ionic solids have high melting points.
2. These solids do not conduct electricity, because the ions
are fixed in their lattice positions.
3. They do conduct electricity in molten state (or) when
dissolved in water because, the ions are free to move in the
molten state or solution.
4. They are hard as only strong external force can change
the relative positions of ions.
Covalent solids:
• In covalent solids, the constituents (atoms) are
bound together in a three dimensional network
entirely by covalent bonds.
• Examples: Diamond, silicon carbide etc.
• Such covalent network crystals are very hard,
and have high melting point.
• They are usually poor thermal and electrical
conductors.
Molecular solids:
• In molecular solids, the constituents are neutral
molecules. They are held together by weak van
der Waals forces.
• Generally molecular solids are soft and they do
not conduct electricity.
• These molecular solids are further classified into
three types.
(i) Non-polar molecular solids
(ii) Polar molecular solids
(iii) Hydrogen bonded molecular solids
Just Known It
• Graphite is used inside pencils.
• It slips easily off the pencil onto the paper and
leaves a blackmark.
• Graphite is also a component of many lubricants
, for example bicycle chain oil , because it is
slippery
Non-polar molecular solids
• In non polar molecular solids constituent molecules are
held together by weak dispersion forces or London forces.
• They have low melting points and are usually in liquids or
gaseous state at room temperature.
• Examples: naphthalene, anthracene etc.,
Polar molecular solids
• The constituents are molecules formed by polar
covalent bonds.
• They are held together by relatively strong dipole -
dipole interactions.
• They have higher melting points than the non-polar
molecular solids. Examples are solid CO2 , solid NH3
etc…,
Hydrogen bonded molecular solids
• The constituents are held together by
hydrogen bonds.
• They are generally soft solids under
room temperature. Examples: solid ice
(H2O), glucose, urea etc.,
Metallic solids:
• In metallic solids, the lattice points are
occupied by positive metal ions and a cloud of
electrons pervades the space.
• They are hard, and have high melting point.
Metallic solids possess excellent electrical and
thermal conductivity. They possess bright
lustre.
Examples: Metals and metal alloys belong to
this type of solids, for example Cu, Fe, Zn, Ag
,Au, CuZn etc.
Crystal lattice and unit cell
• Crystalline solid is characterised by a definite
orientation of atoms, ions or molecules,
relative to one another in a three dimensional
pattern.
• The regular arrangement of these species
throughout the crystal is called a crystal lattice.
• A basic repeating structural unit of a crystalline
solid is called a unit cell.
• The following figure illustrates the lattice point
and the unit cell.
• A crystal may be considered to consist of
large number of unit cells, each one in direct
contact with its nearer neighbour and all
similarly oriented in space.
• The number of nearest neighbours that
surrounding a particle in a crystal is called
the coordination number of that particle.
• A unit cell is characterised by the three edge
lengths or lattice constants a, b and c and the
angle between the edges α, β and γ
Primitive and non-primitive unit cell
• There are two types of unit cells: primitive and non-
primitive.
• A unit cell that contains only one type of lattice point is
called a primitive unit cell, which is made up from the
lattice points at each of the corners.
• In case of non-primitive unit cells, there are additional
lattice points, either on a face of the unit cell or with in
the unit cell.
• There are seven primitive crystal systems; cubic,
tetragonal, orthorhombic, hexagonal, monoclinic,
triclinic and rhombohedral. They differ in the
arrangement of their crystallographic axes and angles.
Corresponding to the above seven, Bravais defined 14
possible crystal systems as shown in the figure.
14 Bravais Lattices
Number of atoms in a cubic unit cell
Primitive (or) simple cubic unit cell(SC)
• In the simple cubic unit cell, each corner is occupied
by an identical atoms or ions or molecules.
• And they touch along the edges of the cube, do not
touch diagonally. The coordination number of each
atom is 6.
• Each atom in the corner of the cubic unit cell is shared
by 8 neighboring unit cells and therefore atoms `per
𝑁𝑐
unit cell is equal to , where Nc is the number of
8
atoms at the corners.
Body centered cubic unit cell. (BCC)
• In a body centered cubic unit cell, each
corner is occupied by an identical particle
and in addition to that one atom occupies the
body centre.
• Those atoms which occupy the corners do
not touch each other, however they all touch
the one that occupies the body centre.
• Hence, each atom is surrounded by eight
nearest neighbours and coordination number
is 8.
• An atom present at the body centre belongs
to only to a particular unit cell i.e unshared
by other unit cell.
Face centered cubic unit cell (FCC)
• In a face centered cubic unit cell, identical atoms
lie at each corner as well as in the centre of each
face.
• Those atoms in the corners touch those in the faces
but not each other.
• The atoms in the face centre is being shared by two
1
unit cells, each atom in the face centers makes
2
contribution to the unit cell.
• Drawing the crystal lattice on paper is not an easy task.
• The constituents in a unit cell touch each other and form
a three dimensional network.
• This can be simplified by drawing crystal structure with
the help of small circles (spheres) corresponding
constituent particles and connecting neighbouring
particles using a straight line as shown in the figure.
Calculations involving unit cell dimensions:
• X-Ray diffraction analysis is the most powerful
tool for the determination of crystal structure.
• The inter planar distance (d) between two
successive planes of atoms can be calculated
using the following equation form the X-Ray
diffraction data 2dsin θ = nλ
Calculation of density
• Using the edge length of a unit cell, we
can calculate the density (ρ) of the
crystal by considering a cubic unit cell
as follows.
Just Think It
• Barium has a body centered cubic unit cell with a
length of 508pm along an edge. What is the density of
barium in g cm-3?
Out of the Box
1. An element has a face centered cubic unit cell
with a length of 352.4 pm along an edge. The
density of the element is 8.9 gcm-3. How many
atoms are present in 100 g of an element?
2. Determine the density of CsCl which
crystallizes in a bcc type structure with an edge
length 412.1 pm.
3. A face centered cubic solid of an element
(atomic mass 60) has a cube edge of 4A .
Calculate its density.
Packing in crystals
• Let us consider the packing of fruits for display in fruit stalls.
They are in a closest packed arrangement as shown in the
following fig.
• we can extend this analogy to visualize the packing of
constituents (atoms / ions / molecules) in crystals, by treating
them as hard spheres.
• To maximize the attractive forces between the constituents, they
generally tend to pack together as close as possible to each other.
• In this portion we discuss how to pack identical spheres to create
cubic and hexagonal unit cell.
• Before moving on to these three dimensional arrangements, let us
first consider the two dimensional arrangement of spheres for
better understanding.
Linear arrangement of spheres in one direction
• In a specific direction, there is only one
possibility to arrange the spheres in one
direction as shown in the fig. in this
arrangement each sphere is in contact with
two neighbouring spheres on either side.
Two dimensional close packing
• Two dimensional planar packing can be
done in the following two different ways.
(i) AAA… type
(i) ABAB.. Type
AAA… type:
• Linear arrangement of spheres in one direction is
repeated in two dimension i.e., more number of rows
can be generated identical to the one dimensional
arrangement such that all spheres of different rows align
vertically as well as horizontally as shown in the fig.
• If we denote the first row as A type arrangement, then
the above mentioned packing is called AAA type,
because all rows are identical as the first one.
• In this arrangement each sphere is in contact with four
of its neighbours.
ABAB.. Type:
• In this type, the second row spheres are arranged in
such a way that they fit in the depression of the first
row as shown in the figure. The second row is
denoted as B type.
• The third row is arranged similar to the first row A,
and the fourth one is arranged similar to second
one. i.e., the pattern is repeated as ABAB….
• In this arrangement each sphere is in contact with 6
of its neighbouring spheres.
• On comparing these two arrangements
(AAAA...type and ABAB….type) we found that the
closest arrangement is ABAB…type.
Simple cubic arrangement:
• This type of three dimensional packing arrangements can
be obtained by repeating the AAAA type two
dimensional arrangements in three dimensions. i.e.,
spheres in one layer sitting directly on the top of those in
the previous layer so that all layers are identical.
• All spheres of different layers of crystal are perfectly
aligned horizontally and also vertically, so that any unit
cell of such arrangement as simple cubic structure as
shown in fig.
• In simple cubic packing, each sphere is in contact with 6
neighbouring spheres - Four in its own layer, one above
and one below and hence the coordination number of the
sphere in simple cubic arrangement is 6.
Packing efficiency
• There is some free space between the spheres
of a single layer and the spheres of successive
layers.
• The percentage of total volume occupied by
these constituent spheres gives the packing
efficiency of an arrangement.
• Let us calculate the packing efficiency in
simple cubic arrangement,
Body centered cubic arrangement
• In this arrangement, the spheres in the first layer ( A
type ) are slightly separated and the second layer is
formed by arranging the spheres in the depressions
between the spheres in layer A as shown in figure.
• The third layer is a repeat of the first. This pattern
ABABAB is repeated throughout the crystal.
• In this arrangement, each sphere has a coordination
number of 8, four neighbors in the layer above and
four in the layer below.
Packing efficiency:
Here, the spheres are touching along the
leading diagonal of the cube as shown in the
fig
The hexagonal and face centered cubic arrangement
Formation of first layer:
In this arrangement, the first layer is formed by
arranging the spheres as in the case of two
dimensional ABAB arrangements i.e. the spheres of
second row fit into the depression of first row.
Now designate this first layer as ‘a’.
The next layer is formed by placing the spheres in
the depressions of the first layer. Let the second
layer be ‘b’.
Formation of second layer:
In the first layer (a) there are two types of voids
(or holes) and they are designated as x and y.
The second layer (b) can be formed by placing
the spheres either on the depression
(voids/holes) x (or) on y.
let us consider the formation of second layer by
placing the spheres on the depression (x).
• Wherever a sphere of second layer (b) is above the
void (x) of the first layer (a), a tetrahedral void is
formed.
• This constitutes four spheres – three in the lower
(a) and one in the upper layer (b).
• When the centers of these four spheres are joined, a
tetrahedron is formed. At the same time, the voids
(y) in the first layer (a) are partially covered by the
spheres of layer (b), now such a void in (a) is called
a octahedral void.
• This constitutes six spheres – three in the lower
layer (a) and three in the upper layer (b).
• When the centers of these six spheres are joined, an
octahedron is formed.
• Simultaneously new tetrahedral voids (or holes) are also
created by three spheres in second layer (b) and one
sphere of first layer (a)
• The number of voids depends on the number of close
packed spheres.
• If the number of close packed spheres be ‘n’ then, the
number of octahedral voids generated is equal to n and
the number of tetrahedral voids generated is equal to 2n.
Formation of third layer
• The third layer of spheres can be formed in two ways
to achieve closest packing
(i) aba arrangement - hcp structure
(ii) abc arrangement – ccp structure
The spheres can be arranged so as to fit into the
depression in such a way that the third layer is directly
over a first layer as shown in the figure.
This “aba’’ arrangement is known as the hexagonal
close packed (hcp) arrangement.
In this arrangement, the tetrahedral voids of the second
layer are covered by the spheres of the third layer..
• Alternatively, the third layer may be placed over
the second layer in such a way that all the spheres
of the third layer fit in octahedral voids.
• This arrangement of the third layer is different
from other two layers (a) and (b), and hence, the
third layer is designated (c).
• If the stacking of layers is continued in
abcabcabc… pattern, then the arrangement is
called cubic close packed (ccp) structure.
• In both hcp and ccp arrangements, the
coordination number of each sphere is 12 –
six neighbouring spheres in its own layer,
three spheres in the layer above and three
sphere in the layer below.
• This is the most efficient packing.
Packing Efficiency
• The cubic close packing is based on the
face centered cubic unit cell. Let us
calculate the packing efficiency in fcc unit
cell.
Radius ratio
• The structure of an ionic compound depends
upon the stoichiometry and the size of the ions.
• generally in ionic crystals the bigger anions are
present in the close packed arrangements and the
cations occupy the voids.
• The ratio of radius of cation and anion rc+\ra-
plays an important role in determining the
structure.
The following table shows the relation between the radius ratio and the
structural arrangement in ionic solids.
Coordination
Radius Ratio Range Structure Example
Number
Trigonal
0.155 – 0.225 3 B₂O₃
planar
0.225 – 0.414 4 Tetrahedral ZnS
0.414 – 0.732 6 Octahedral NaCl
0.732 – 1.0 8 Cubic CsCl
Imperfection in solids
• According to the law of nature nothing is perfect, and
so crystals need not be perfect.
• They always found to have some defects in the
arrangement of their constituent particles.
• These defects affect the physical and chemical
properties of the solid and also play an important role
in various processes.
• For example, a process called doping leads to a
crystal imperfection and it increases the electrical
conductivity of a semiconductor material such as
silicon.
• The ability of ferromagnetic material such as iron,
nickel etc., to be magnetized and demagnetized
depends on the presence of imperfections.
• Crystal defects are classified as follows
1) Point defects
2) Line defects
3) Interstitial defects
4) Volume defects
• In this portion, we concentrate on point defects,
more specifically in ionic solids.
Stoichiometric defects in ionic solid
• This defect is also called intrinsic (or)
thermodynamic defect.
• In stoichiometric ionic crystals, a vacancy of one
ion must always be associated with either by the
absence of another oppositely charged ion (or) the
presence of same charged ion in the interstitial
position so as to maintain the electrical neutrality.
Schottky defect
• Schottky defect arises due to the missing of equal number of
cations and anions from the crystal lattice.
• This effect does not change the stoichiometry of the crystal.
Ionic solids in which the cation and anion are of almost of
similar size show Schottky defect.
• Example: NaCl. Presence of large number of Schottky
defects in a crystal, lowers its density.
• For example, the theoretical density of vanadium monoxide
(VO) calculated using the edge length of the unit cell is 6.5 g
cm-3, but the actual experimental density is 5.6 g cm-3.
• It indicates that there is approximately
14% Schottky defect in VO crystal.
• Presence of Schottky defect in the
crystal provides a simple way by
which atoms or ions can move within
the crystal lattice.
Frenkel defect
• Frenkel defect arises due to the dislocation of ions from its
crystal lattice.
• The ion which is missing from the lattice point occupies an
interstitial position.
• This defect is shown by ionic solids in which cation and
anion differ in size.
• Unlike Schottky defect, this defect does not affect the
density of the crystal.
• For example AgBr, in this case, small Ag+ ion leaves its
normal site and occupies an interstitial position as shown in
the figure.
Metal excess defect
• Metal excess defect arises due to the presence of
more number of metal ions as compared to anions.
• Alkali metal halides NaCl, KCl show this type of
defect.
• The electrical neutrality of the crystal can be
maintained by the presence of anionic vacancies
equal to the excess metal ions (or) by the presence
of extra cation and electron present in interstitial
position.
• For example, when NaCl crystals are heated in the presence
of sodium vapour, Na+ ions are formed and are deposited on
the surface of the crystal.
• Chloride ions (Cl- ) diffuse to the surface from the lattice
point and combines with Na+ ion.
• The electron lost by the sodium vapour diffuse into the
crystal lattice and occupies the vacancy created by the Cl-
ions.
• Such anionic vacancies which are occupied by unpaired
electrons are called F centers.
• Hence, the formula of NaCl which contains excess Na+ ions
can be written as Na1+ x Cl.
• ZnO is colourless at room temperature.
• When it is heated, it becomes yellow in colour.
On heating, it loses oxygen and thereby forming
free Zn2+ ions.
• The excess Zn2+ ions move to interstitial sites
and the electrons also occupy the interstitial
positions.
Metal deficiency defect
• Metal deficiency defect arises due to the presence of less
number of cations than the anions.
• This defect is observed in a crystal in which, the cations
have variable oxidation states.
• For example, in FeO crystal, some of the Fe2+ ions are
missing from the crystal lattice.
• To maintain the electrical neutrality, twice the number of
other Fe2+ ions in the crystal is oxidized to Fe3+ ions. In such
cases, overall number of Fe2+ and Fe3+ ions is less than the
O2- ions.
• It was experimentally found that the general formula of
ferrous oxide is FexO, where x ranges from 0.93 to 0.98.
Impurity defect
• A general method of introducing defects in ionic solids is by
adding impurity ions.
• If the impurity ions are in different valance state from that of
host, vacancies are created in the crystal lattice of the host.
• For example, addition of CdCl2 to AgCl yields solid solutions
where the divalent cation Cd2+ occupies the position of Ag+.
• This will disturb the electrical neutrality of the crystal.
• In order to maintain the same, proportional number of Ag+ ions
leaves the lattice.
• produces a cation vacancy in the lattice, such kind of crystal
defects are called impurity defects.
Just known it
• Energy harvesting by piezoelectric crystals: Piezoelectricity (also
called the piezoelectric effect) is the appearance of an electrical
potential across the sides of a crystal when you subject it to
mechanical stress.
• The word piezoelectricity means electricity resulting from pressure
and latent heat.
• Even the inverse is possible which is known as inverse piezoelectric
effect.
• If you can make a little amount of electricity by
pressing one piezoelectric crystal once, could you
make a significant amount by pressing many crystals
over and over again? What happens if we bury
piezoelectric crystals under streets to capture energy as
vehicles pass by?
• This idea, known as energy harvesting, has caught
many people's interest.
• Even though there are limitations for the large-scale
applications, you can produce electricity that is enough
to charge your mobile phones by just walking.
• There are power generating footwears that has a slip-on
insole with piezoelectric crystals that can produce
enough electricity to charge batteries/ USB devices.
 12th CHEMISTRY

6.SOLID STATE
INTRODUCTION
• Solids differ from liquids and gases by
possessing definite volume and definite
shape.
• In the solids the atoms or molecules or ion
are tightly held in an ordered arrangement
and there are many types of solids such as
diamond, metals, plastics etc.,
General characteristics of solids
• The general characteristics of solids are as follows,
(i) Solids have definite volume and shape.
(ii) Solids are rigid and incompressible
(iii) Solids have strong cohesive forces.
(iv) Solids have short inter atomic, ionic or molecular
distances.
(v) Their constituents ( atoms , ions ormolecules) have
fixed positions and can only oscillate about their mean
positions
Classification of solids:
Ionic crystals
(Ex: NaCl,KCl)

Covalent crystals
(Ex: Diamond, SiO2)

Molecular crystals
Crystalline
solids (Ex: naphthalene,
Classification of anthacene, glucose)

solids Metallic crystals

(All Metallic
Amorphous Elements(Na, Mg, Cu,
solids Au, Ag))
(Ex: NaCl, KCl)
Atomic solids(Ex:
Frozen Elements of
group 18 )
• We can classify solids into the following two major
types based on the arrangement of their constituents.
(i) Crystalline solids
(ii) Amorphous solids.
• The term crystal comes from the Greek word
“krystallos” which means clear ice.
• A crystalline solid is one in which its
constituents (atoms, ions or molecules), have an
orderly arrangement extending over a long
range.
• The arrangement of such constituents in a
crystalline solid is such that the potential energy
of the system is at minimum.
The following table shows the differences between crystalline and
amorphous solids
S. No Crystalline Solids Amorphous Solids
Long-range orderly arrangement of
1 Short-range, random arrangement of constituents.
constituents.
2 Definite shape. Irregular shape.
Generally crystalline solids are anisotropic
3 They are isotropic, like liquids.
in nature.

They are considered pseudo solids or supercooled

4 They are true solids.
liquids.
5 Definite heat of fusion. Heat of fusion is not definite.
Gradually soften over a range of temperature and can
6 They have sharp melting points.
be molded.
7 Examples: NaCl, diamond, etc. Examples: Rubber, plastics, glass, etc.
Isotropy
• Isotropy means uniformity in all directions.
• In solid state isotropy means having identical values of physical properties such
as refractive index, electrical conductance etc., in all directions, whereas
anisotropy is the property which depends on the direction of measurement.
• Crystalline solids are anisotropic and they show
different values of physical properties when
measured along different directions.
Classification of crystalline solids
Ionic solids:
• The structural units of an ionic crystal are
cations and anions. They are bound together by
strong electrostatic attractive forces.
• To maximize the attractive force, cations are
surrounded by as many anions as possible and
vice versa.
Ionic crystals possess definite crystal structure; many solids are
cubic close packed.
Example: The arrangement of Na+ and Cl- ions in NaCl crystal.
Characteristics:
1. Ionic solids have high melting points.
2. These solids do not conduct electricity, because the ions
are fixed in their lattice positions.
3. They do conduct electricity in molten state (or) when
dissolved in water because, the ions are free to move in the
molten state or solution.
4. They are hard as only strong external force can change
the relative positions of ions.
Covalent solids:
• In covalent solids, the constituents (atoms) are
bound together in a three dimensional network
entirely by covalent bonds.
• Examples: Diamond, silicon carbide etc.
• Such covalent network crystals are very hard,
and have high melting point.
• They are usually poor thermal and electrical
conductors.
Molecular solids:
• In molecular solids, the constituents are neutral
molecules. They are held together by weak van
der Waals forces.
• Generally molecular solids are soft and they do
not conduct electricity.
• These molecular solids are further classified into
three types.
(i) Non-polar molecular solids
(ii) Polar molecular solids
(iii) Hydrogen bonded molecular solids
Non-polar molecular solids
• In non polar molecular solids constituent molecules are
held together by weak dispersion forces or London forces.
• They have low melting points and are usually in liquids or
gaseous state at room temperature.
• Examples: naphthalene, anthracene etc.,
Polar molecular solids
• The constituents are molecules formed by polar
covalent bonds.
• They are held together by relatively strong dipole -
dipole interactions.
• They have higher melting points than the non-polar
molecular solids. Examples are solid CO2 , solid NH3
etc…,
Hydrogen bonded molecular solids
• The constituents are held together by
hydrogen bonds.
• They are generally soft solids under
room temperature. Examples: solid ice
(H2O), glucose, urea etc.,
Metallic solids:
• In metallic solids, the lattice points are
occupied by positive metal ions and a cloud of
electrons pervades the space.
• They are hard, and have high melting point.
Metallic solids possess excellent electrical and
thermal conductivity. They possess bright
lustre.
Examples: Metals and metal alloys belong to
this type of solids, for example Cu, Fe, Zn, Ag
,Au, CuZn etc.
Crystal lattice and unit cell
• Crystalline solid is characterised by a definite
orientation of atoms, ions or molecules,
relative to one another in a three dimensional
pattern.
• The regular arrangement of these species
throughout the crystal is called a crystal lattice.
• A basic repeating structural unit of a crystalline
solid is called a unit cell.
• The following figure illustrates the lattice point
and the unit cell.
• A crystal may be considered to consist of
large number of unit cells, each one in direct
contact with its nearer neighbour and all
similarly oriented in space.
• The number of nearest neighbours that
surrounding a particle in a crystal is called
the coordination number of that particle.
• A unit cell is characterised by the three edge
lengths or lattice constants a, b and c and the
angle between the edges α, β and γ
Primitive and non-primitive unit cell
• There are two types of unit cells: primitive and non-
primitive.
• A unit cell that contains only one type of lattice point is
called a primitive unit cell, which is made up from the
lattice points at each of the corners.
• In case of non-primitive unit cells, there are additional
lattice points, either on a face of the unit cell or with in
the unit cell.
• There are seven primitive crystal systems; cubic,
tetragonal, orthorhombic, hexagonal, monoclinic,
triclinic and rhombohedral. They differ in the
arrangement of their crystallographic axes and angles.
Corresponding to the above seven, Bravais defined 14
possible crystal systems as shown in the figure.
14 Bravais Lattices
Number of atoms in a cubic unit cell
Primitive (or) simple cubic unit cell(SC)
• In the simple cubic unit cell, each corner is occupied
by an identical atoms or ions or molecules.
• And they touch along the edges of the cube, do not
touch diagonally. The coordination number of each
atom is 6.
• Each atom in the corner of the cubic unit cell is shared
by 8 neighboring unit cells and therefore atoms `per
𝑁𝑐
unit cell is equal to , where Nc is the number of
8
atoms at the corners.
Body centered cubic unit cell. (BCC)
• In a body centered cubic unit cell, each
corner is occupied by an identical particle
and in addition to that one atom occupies the
body centre.
• Those atoms which occupy the corners do
not touch each other, however they all touch
the one that occupies the body centre.
• Hence, each atom is surrounded by eight
nearest neighbours and coordination number
is 8.
• An atom present at the body centre belongs
to only to a particular unit cell i.e unshared
by other unit cell.
Face centered cubic unit cell (FCC)
• In a face centered cubic unit cell, identical atoms
lie at each corner as well as in the centre of each
face.
• Those atoms in the corners touch those in the faces
but not each other.
• The atoms in the face centre is being shared by two
1
unit cells, each atom in the face centers makes
2
contribution to the unit cell.
• Drawing the crystal lattice on paper is not an easy task.
• The constituents in a unit cell touch each other and form
a three dimensional network.
• This can be simplified by drawing crystal structure with
the help of small circles (spheres) corresponding
constituent particles and connecting neighbouring
particles using a straight line as shown in the figure.
Calculations involving unit cell dimensions:
• X-Ray diffraction analysis is the most powerful
tool for the determination of crystal structure.
• The inter planar distance (d) between two
successive planes of atoms can be calculated
using the following equation form the X-Ray
diffraction data 2dsin θ = nλ
Calculation of density
• Using the edge length of a unit cell, we
can calculate the density (ρ) of the
crystal by considering a cubic unit cell
as follows.
Just Think It
• Barium has a body centered cubic unit cell with a
length of 508pm along an edge. What is the density of
barium in g cm-3?
Out of the Box
1. An element has a face centered cubic unit cell
with a length of 352.4 pm along an edge. The
density of the element is 8.9 gcm-3. How many
atoms are present in 100 g of an element?
2. Determine the density of CsCl which
crystallizes in a bcc type structure with an edge
length 412.1 pm.
3. A face centered cubic solid of an element
(atomic mass 60) has a cube edge of 4A .
Calculate its density.
Packing in crystals
• Let us consider the packing of fruits for display in fruit stalls.
They are in a closest packed arrangement as shown in the
following fig.
• we can extend this analogy to visualize the packing of
constituents (atoms / ions / molecules) in crystals, by treating
them as hard spheres.
• To maximize the attractive forces between the constituents, they
generally tend to pack together as close as possible to each other.
• In this portion we discuss how to pack identical spheres to create
cubic and hexagonal unit cell.
• Before moving on to these three dimensional arrangements, let us
first consider the two dimensional arrangement of spheres for
better understanding.
Linear arrangement of spheres in one direction
• In a specific direction, there is only one
possibility to arrange the spheres in one
direction as shown in the fig. in this
arrangement each sphere is in contact with
two neighbouring spheres on either side.
Two dimensional close packing
• Two dimensional planar packing can be
done in the following two different ways.
(i) AAA… type
(i) ABAB.. Type
AAA… type:
• Linear arrangement of spheres in one direction is
repeated in two dimension i.e., more number of rows
can be generated identical to the one dimensional
arrangement such that all spheres of different rows align
vertically as well as horizontally as shown in the fig.
• If we denote the first row as A type arrangement, then
the above mentioned packing is called AAA type,
because all rows are identical as the first one.
• In this arrangement each sphere is in contact with four
of its neighbours.
ABAB.. Type:
• In this type, the second row spheres are arranged in
such a way that they fit in the depression of the first
row as shown in the figure. The second row is
denoted as B type.
• The third row is arranged similar to the first row A,
and the fourth one is arranged similar to second
one. i.e., the pattern is repeated as ABAB….
• In this arrangement each sphere is in contact with 6
of its neighbouring spheres.
• On comparing these two arrangements
(AAAA...type and ABAB….type) we found that the
closest arrangement is ABAB…type.
Simple cubic arrangement:
• This type of three dimensional packing arrangements can
be obtained by repeating the AAAA type two
dimensional arrangements in three dimensions. i.e.,
spheres in one layer sitting directly on the top of those in
the previous layer so that all layers are identical.
• All spheres of different layers of crystal are perfectly
aligned horizontally and also vertically, so that any unit
cell of such arrangement as simple cubic structure as
shown in fig.
• In simple cubic packing, each sphere is in contact with 6
neighbouring spheres - Four in its own layer, one above
and one below and hence the coordination number of the
sphere in simple cubic arrangement is 6.
Packing efficiency
• There is some free space between the spheres
of a single layer and the spheres of successive
layers.
• The percentage of total volume occupied by
these constituent spheres gives the packing
efficiency of an arrangement.
• Let us calculate the packing efficiency in
simple cubic arrangement,
Body centered cubic arrangement
• In this arrangement, the spheres in the first layer ( A
type ) are slightly separated and the second layer is
formed by arranging the spheres in the depressions
between the spheres in layer A as shown in figure.
• The third layer is a repeat of the first. This pattern
ABABAB is repeated throughout the crystal.
• In this arrangement, each sphere has a coordination
number of 8, four neighbors in the layer above and
four in the layer below.
Packing efficiency:
Here, the spheres are touching along the
leading diagonal of the cube as shown in the
fig
The hexagonal and face centered cubic arrangement
Formation of first layer:
In this arrangement, the first layer is formed by
arranging the spheres as in the case of two
dimensional ABAB arrangements i.e. the spheres of
second row fit into the depression of first row.
Now designate this first layer as ‘a’.
The next layer is formed by placing the spheres in
the depressions of the first layer. Let the second
layer be ‘b’.
Formation of second layer:
In the first layer (a) there are two types of voids
(or holes) and they are designated as x and y.
The second layer (b) can be formed by placing
the spheres either on the depression
(voids/holes) x (or) on y.
let us consider the formation of second layer by
placing the spheres on the depression (x).
• Wherever a sphere of second layer (b) is above the
void (x) of the first layer (a), a tetrahedral void is
formed.
• This constitutes four spheres – three in the lower
(a) and one in the upper layer (b).
• When the centers of these four spheres are joined, a
tetrahedron is formed. At the same time, the voids
(y) in the first layer (a) are partially covered by the
spheres of layer (b), now such a void in (a) is called
a octahedral void.
• This constitutes six spheres – three in the lower
layer (a) and three in the upper layer (b).
• When the centers of these six spheres are joined, an
octahedron is formed.
• Simultaneously new tetrahedral voids (or holes) are also
created by three spheres in second layer (b) and one
sphere of first layer (a)
• The number of voids depends on the number of close
packed spheres.
• If the number of close packed spheres be ‘n’ then, the
number of octahedral voids generated is equal to n and
the number of tetrahedral voids generated is equal to 2n.
Formation of third layer
• The third layer of spheres can be formed in two ways
to achieve closest packing
(i) aba arrangement - hcp structure
(ii) abc arrangement – ccp structure
The spheres can be arranged so as to fit into the
depression in such a way that the third layer is directly
over a first layer as shown in the figure.
This “aba’’ arrangement is known as the hexagonal
close packed (hcp) arrangement.
In this arrangement, the tetrahedral voids of the second
layer are covered by the spheres of the third layer..
• Alternatively, the third layer may be placed over
the second layer in such a way that all the spheres
of the third layer fit in octahedral voids.
• This arrangement of the third layer is different
from other two layers (a) and (b), and hence, the
third layer is designated (c).
• If the stacking of layers is continued in
abcabcabc… pattern, then the arrangement is
called cubic close packed (ccp) structure.
• In both hcp and ccp arrangements, the
coordination number of each sphere is 12 –
six neighbouring spheres in its own layer,
three spheres in the layer above and three
sphere in the layer below.
• This is the most efficient packing.
Packing Efficiency
• The cubic close packing is based on the
face centered cubic unit cell. Let us
calculate the packing efficiency in fcc unit
cell.
Radius ratio
• The structure of an ionic compound depends
upon the stoichiometry and the size of the ions.
• generally in ionic crystals the bigger anions are
present in the close packed arrangements and the
cations occupy the voids.
• The ratio of radius of cation and anion rc+\ra-
plays an important role in determining the
structure.
The following table shows the relation between the radius ratio and the
structural arrangement in ionic solids.
Coordination
Radius Ratio Range Structure Example
Number
Trigonal
0.155 – 0.225 3 B₂O₃
planar
0.225 – 0.414 4 Tetrahedral ZnS
0.414 – 0.732 6 Octahedral NaCl
0.732 – 1.0 8 Cubic CsCl
Imperfection in solids
• According to the law of nature nothing is perfect, and
so crystals need not be perfect.
• They always found to have some defects in the
arrangement of their constituent particles.
• These defects affect the physical and chemical
properties of the solid and also play an important role
in various processes.
• For example, a process called doping leads to a
crystal imperfection and it increases the electrical
conductivity of a semiconductor material such as
silicon.
• The ability of ferromagnetic material such as iron,
nickel etc., to be magnetized and demagnetized
depends on the presence of imperfections.
• Crystal defects are classified as follows
1) Point defects
2) Line defects
3) Interstitial defects
4) Volume defects
• In this portion, we concentrate on point defects,
more specifically in ionic solids.
Stoichiometric defects in ionic solid
• This defect is also called intrinsic (or)
thermodynamic defect.
• In stoichiometric ionic crystals, a vacancy of one
ion must always be associated with either by the
absence of another oppositely charged ion (or) the
presence of same charged ion in the interstitial
position so as to maintain the electrical neutrality.
Schottky defect
• Schottky defect arises due to the missing of equal number of
cations and anions from the crystal lattice.
• This effect does not change the stoichiometry of the crystal.
Ionic solids in which the cation and anion are of almost of
similar size show Schottky defect.
• Example: NaCl. Presence of large number of Schottky
defects in a crystal, lowers its density.
• For example, the theoretical density of vanadium monoxide
(VO) calculated using the edge length of the unit cell is 6.5 g
cm-3, but the actual experimental density is 5.6 g cm-3.
• It indicates that there is approximately
14% Schottky defect in VO crystal.
• Presence of Schottky defect in the
crystal provides a simple way by
which atoms or ions can move within
the crystal lattice.
Frenkel defect
• Frenkel defect arises due to the dislocation of ions from its
crystal lattice.
• The ion which is missing from the lattice point occupies an
interstitial position.
• This defect is shown by ionic solids in which cation and
anion differ in size.
• Unlike Schottky defect, this defect does not affect the
density of the crystal.
• For example AgBr, in this case, small Ag+ ion leaves its
normal site and occupies an interstitial position as shown in
the figure.
Metal excess defect
• Metal excess defect arises due to the presence of
more number of metal ions as compared to anions.
• Alkali metal halides NaCl, KCl show this type of
defect.
• The electrical neutrality of the crystal can be
maintained by the presence of anionic vacancies
equal to the excess metal ions (or) by the presence
of extra cation and electron present in interstitial
position.
• For example, when NaCl crystals are heated in the presence
of sodium vapour, Na+ ions are formed and are deposited on
the surface of the crystal.
• Chloride ions (Cl- ) diffuse to the surface from the lattice
point and combines with Na+ ion.
• The electron lost by the sodium vapour diffuse into the
crystal lattice and occupies the vacancy created by the Cl-
ions.
• Such anionic vacancies which are occupied by unpaired
electrons are called F centers.
• Hence, the formula of NaCl which contains excess Na+ ions
can be written as Na1+ x Cl.
• ZnO is colourless at room temperature.
• When it is heated, it becomes yellow in colour.
On heating, it loses oxygen and thereby forming
free Zn2+ ions.
• The excess Zn2+ ions move to interstitial sites
and the electrons also occupy the interstitial
positions.
Metal deficiency defect
• Metal deficiency defect arises due to the presence of less
number of cations than the anions.
• This defect is observed in a crystal in which, the cations
have variable oxidation states.
• For example, in FeO crystal, some of the Fe2+ ions are
missing from the crystal lattice.
• To maintain the electrical neutrality, twice the number of
other Fe2+ ions in the crystal is oxidized to Fe3+ ions. In such
cases, overall number of Fe2+ and Fe3+ ions is less than the
O2- ions.
• It was experimentally found that the general formula of
ferrous oxide is FexO, where x ranges from 0.93 to 0.98.
Impurity defect
• A general method of introducing defects in ionic solids is by
adding impurity ions.
• If the impurity ions are in different valance state from that of
host, vacancies are created in the crystal lattice of the host.
• For example, addition of CdCl2 to AgCl yields solid solutions
where the divalent cation Cd2+ occupies the position of Ag+.
• This will disturb the electrical neutrality of the crystal.
• In order to maintain the same, proportional number of Ag+ ions
leaves the lattice.
• produces a cation vacancy in the lattice, such kind of crystal
defects are called impurity defects.
Just known it
• Energy harvesting by piezoelectric crystals: Piezoelectricity (also
called the piezoelectric effect) is the appearance of an electrical
potential across the sides of a crystal when you subject it to
mechanical stress.
• The word piezoelectricity means electricity resulting from pressure
and latent heat.
• Even the inverse is possible which is known as inverse piezoelectric
effect.
• If you can make a little amount of electricity by
pressing one piezoelectric crystal once, could you
make a significant amount by pressing many crystals
over and over again? What happens if we bury
piezoelectric crystals under streets to capture energy as
vehicles pass by?
• This idea, known as energy harvesting, has caught
many people's interest.
• Even though there are limitations for the large-scale
applications, you can produce electricity that is enough
to charge your mobile phones by just walking.
• There are power generating footwears that has a slip-on
insole with piezoelectric crystals that can produce
enough electricity to charge batteries/ USB devices.