Solid State
Solid State
Solid State
BASICS Section - 1
1.1 Introduction :
A matter is said to be solid when its constituent particles (atoms, molecules, or ions) are closely packed. A
solid is also defined as that form of matter which possesses rigidity and hence possesses a definite shape and
a definite volume. Unlike gases and liquids, whose fluidity is determined by the relative free motion of their
molecules, in solids, on the contrary, molecules or atoms or ions are not free to move but can oscillate
around their fixed positions due to strong inetermolecular or inter-atomic or inter-ionic forces. This confers
rigidity and long range order in solids.
1. Crystalline Solids
The substances whose constituents are arranged in definite orderly arrangement are called crystalline
solids. Many naturally occurring solid substances occur in the crystalline form. Some common examples
of crystalline solids are sodium chloride, diamond, sugar, etc.
2. Amorphous Solids
An amorphous solid is a substance whose constituent particles do not possess a regular orderly arrangement
e.g. glass, plastics, rubber, starch, and proteins. Though amorphous solids do not possess long range regularity,
in some cases they may possess small regions of orderly arrangement. These crystalline parts of an otherwise
amorphous solid are known as crystallites.
An amorphous solid does not posses a sharp melting point. It undergoes liquefication over abroad range of
temperature. When an amorphous solid is cut with the help of sharp edged knife, it results in a irregular cut.
Amorphous substances are also, sometimes, referred to as super cooled liquids because they possess
disorderly arrangement like liquids. In fact many amorphous solids such as glass are capable flowing. Care-
ful examination of the window panes of very old houses reveals that the panes are thicker at the bottom than
at the top because the glass has flown under constant influence of gravity
Melting Point They have sharp melting points. They do not have sharp melting points.
Heat of Fusion They have characteristic heat of fusion. They do not have characteristic heat of
fusion.
Physical state Crystalline solids are hard and rigid and their Amorphous solid are comparatively soft and
shape is not distroted by mild distorting forces. not very rigid. These can be distorted by
bending or compressing forces.
Crystalline solids are anisotropic. This implies Amorphous solids are isotropic in nature.
Anisotropic or that physical properties such as refractive index This implies that various physical properties
(e.g. Canada Balsam), conductivity, thermal ex- are same in all the directions. This is because
Isotropic nature pansion etc are different in different directions. of random arrangement of particles.
This is due to orderly arrangement of particles
Note : Some substances adopt different structural arrangements under different conditions, Such
compounds are called as polymorphs. These different structures have different properties
such as melting point, density etc.
Example : Diamond and graphite two differnt polymorphic forms of carbon.
Though shown in two dimensions this systematic long-range order is also found in three dimensions, with
each Na+ surrounded by six Cl- ions and vice versa. This order is due to strong coulombic forces of
attraction between Na+ and Cl- ions. Similar regular arrangements are found in other solids too.
In a crystalline solid, the constituent particles (atoms, ions or molecules) arranged in a regular order. An
interaction of a particular crystalline solid with X-rays helps in investigating its actual structure.
Crystals are found to act as diffraction grating for X-ray and this indicates that the constituent particles in the
crystals are arranged in planes at close distances in repeating patterns.
Suppose two waves (Y and Z) of X-ray beams, which are in phase fall on the surface of the crystal. If the
ray Y get reflected from the first layer i.e., AB line and the ray Z is reflected from the second layer of atoms
i.e., CD line, then it is evident that as compared to the ray Y, ray Z has to travel a longer distance, equal to
QRS in order to emerge out of the crystal. If the waves Y and Z are in-phase (for intensity of the reflected
beam to be maximum) after reflection, the difference in distance travelled by the two ray must be equal to an
integral multiple of wavelength i.e., n (for constructive interference).
Thus,
= Angle between incident X-ray and plane of the crystal. The diffracted beam makes an angle 2.
n = An integer (1, 2, 3, 4, etc.) which represents the serial order of diffracted beams.
For given set of lattice planes, d has a fixed value. Therefore, the possibility of getting maximum reflection
(i.e., the possibility of getting reflected waves in phase with one another) depends upon . If is increased
gradually, a number of positions will be found at which the reflections will be maximum. At these positions,
n will have values equal to 1, 2, 3, 4, 5 etc. Generally, in experiments on X-ray reflections, n is set equal to
1. If is known, it is possible to determine d, the distance between atomic planes in the crystal by determining
experimentally. Similarly, if interplanar distance are given, the corresponding wavelengths of the incident
beam of X-ray can be calculated.
2 = 14.66 or = 7.33
n 2 70.93 1012
Therefore, d= = m = 556.3 1012 = 556.3 pm
2sin 2sin 7.33
Before discussing the periodic pattern of atomic arrangements in crystals, we need to look into arrangements
of points in space in periodically repeating patterns. This leads us to the concept of a space lattice. A space
lattice provides the framework with reference to which a crystal structure can be described.
Consider the immediate surroundings of a point in the array. If we look due north or due east from this point,
we see another point at a distance of 1 unit. Along northeast, we see the nearest point at a distance 2 units
and long north-northeast, the nearest point is at a distance of 5 units. As this is ture of every point in the
array, the array satisfies the definition given above and can be called a two-dimensional square lattice.
Note : We can have square lattice, hexagonal lattice but pentagonal lattice is not possible because the interior
angle of a regular pentagon is 108o Which is not an integral factor of 360o.
From the complete space lattice, it is possible to select a smallest three dimensional portion which repeats
itself in different directions to generate the complete space lattice. This is called a Unit Cell. In the above
example of the square lattice, the unit cell is the square obtained by joining four neighbouring lattice points,
as shown in figure on last page. Since every corner of this square is common to four unit cell meeting at that
corner, the effective number of lattice points in the unit cell is only one. Alternatively, the unit cell can be
visualized with one lattice point at the centre of the square and with none at the corners (see figure on
previous page)
The regular pattern of wagons below can be described by placing a lattice point at the same place in each
wagon. The arrangement of dots is the lattice, which has a given repeat distance. The motif is the wagon.
The pattern is recovered by stamping the motif on each lattice point.
The motif/basic can be single atom or groups of atoms. But in many elemental crystals, the basis is simple
and consists of one atom per lattice point. In such cases, the crystal is generated by just positioning one
atom of the element at each lattice point. For example, the crystal structure of chromium and copper are
generated as :
These crystals are called monoatomic crystals, to denote the fact that the basis is one atom per lattice
point. ABCC crystal means a monoatomic BCC crystal, unless otherwise stated.
In principle, an infinite number of crystal structure can be generated by combing different bases and different
lattice parameters with the same space lattice. In figure, three different base are combined with the simple
cubic lattice. In figure (a), the crystal is monoatomic, with just one atom at each lattice point. For clarity,
neighbouring atoms are shown separately. Figure (b) illustrates a molecular crystal, with a diatomic molecule
at each lattice point. The centre of the larger atom of the molecule coincides with a lattice point, while the
smaller atom is not at a lattice point. In molecular crystals, the basis is fully defined by giving the number and
types of atoms, the internuclear distance of separation between neighbours molecule and the orientation of
the molecule in relation to the unit cell. In figure (c), the corner atoms of the cube are of one type, but the
atom at the body centre is of different type. The basis is two atoms, the larger one in this case at a lattice
point and the smaller one positioned half-way along the body diagonal, at the body centre, which is not a
lattic point. In the crystal, of course, the unit cell can be shifted such that the body centre becomes a lattice
point and the body corners are no longer lattice points. This crystal should not be confused with monoatomic
BCC crystal, where the body corner and the body centre atom are of the same type.
Illustration - 2 Draw two dimensional Hexagonal Lattice. Try to visualize the possibility of pentagonal
two dimensional lattice.
SOLUTION :
Three regular hexagons intersect at one point. So, in this tow-dimensional lattice, this lattice point is shared
by three unit cell.
1
So, effective no. of lattice points per unit cell 6 1 1 3
3
A regular pentagon has an interior angle of 108o. As 360o is not an integral multiple of 108o, pentagons
cannot be made to meet at a point bearing a constant angle to one another. Hence, a pentagonal lattice is not
possible. On the other hand, a square or a hexagonal two-dimensional lattice is possible as their internal
angles add up to give 360o.
Note : You are advised to read this section again after Section 5 and then proceed further.
The axes of symmetry are called diad, triad, tetrad and hexad, respectively, if the original appearance is
repeated twice (after an angle of 180o), Thirce (after an angle of 120o), four times (after an angle of 90o) and
six times (after an angle of 60o) in one rotation. These axes of symmetry are also called two-fold, three-fold,
four-fold and six-fold, respectively.
360
In general, if the same appearance of a crystal is repeated on rotating through an angle , of around an
n
imaginary axis, the axis is called an n-fold axis.
On the basis of symmetry, viz., Translational, Rotational and Reflection, in total only fourteen 3-D lattices
are possible. These are called Bravais Lattices. These are categorized under 7 crystal systems. Before
going into their detail, lets take a look at the types of unit cells.
2. A point along an edge is shared by four unit cells and only one-fourth of it lies within any one cell.
3. A face-centred point is shared by two unit cell and only one half of it is present in a given unit cell.
4. A body-centred point lies entirely within the unit cell and contributes one complete point to the cell.
ne n n n
Total number of atoms in unit cell = + f + i + e
8 2 1 4
When nc : Number of atom at the corners of the unit cell
nf : Number of atoms at six faces of the unit cell
ni : Number of atoms completely inside the unit cell
ne : Number of atoms at the edge centres of the unit cell
5. Relation between edge length of unit cell and radius of constituent particles.
Each corner atom is in contact with its adjacent corner atom such that
a
2R = a R =
2
6. Rank of the unit cell (z) : Effective number of constituent particles per unit cell.
1 1
z = nc = 8 =1
8 8
7. Number of nearest neighbours or Co-ordination number.
(i) Number of nearest neighbours (NNs) :
It is number of neighbouring constituent
particles that are in close contact with
given constitueat particles.
8. Packing Efficiency :
Note : FCC unit cell can be ideal FCC and pseudo FCC. In pseudo
FCC constituents at corner lattice points are different from
the face centre lattice points.
Note : Face centre constituent particle is in close contact with constituent particle at corners.
Face centre constituent of adjacent faces are in contact with each other.
a
Note : Each face centre touches other face centre atoms (at a distance of ) provided they are not the centres
2
of opposite faces.
6. Rank of the unit cell (z) : Effective number of constituent particles per unit cell.
1 1
Z= No. of corner + No. of face centres
8 2
1 1
= 8 6 1 3 4
8 2
7. Number of nearest (Co-ordination Number)
Consitituent particles at corners are nearest neighbours of the consitituent particle at face centre of the
FCC unit cell.
4 3 4
Z r 4 r3
8. Packing efficiency = 3 = 3 = 0.74
3 3
a 4r
2
Note : In single FCC unit cell there are total 14 constituent particles present at different lattice points.
2
(i) No. of nearest neighbours (NNs) at a distance from particles under observation are three.
2
(ii) No. of next nearest neighbor (NNNs) at a distance from particle under observation are three.
3
(iii) No. of next to next nearest neighbours (NNNNs) at a distance from particle under observation
2
are three.
2a
No of atoms at distance (NNs) are 3. [9, 10, 13]
2
No. of atoms at distance a (NNNs) are 3 [2, 4, 5]
3
No. of atoms at distance a (NNNNs) are 3 [11, 12, 14]
2
No. of atom at distance 2 a are 3 [3, 6, 7]
VOIDS Section - 8
In close packing of spheres, there is always some empty space left. The empty space is called hole or void
or interstitial site. There are two main types of interstitial voids in closely packed structures :
(a) Tetrahedral voids (b) Octahedral voids
Tetrahedral void : When one sphere is placed upon the three other
spheres which are touching each other, tetrahedral structure results. The
name tetrahedral void comes from the regular tetrahedron obtained by
joining the centres of four spheres. The four spheres leave a small space
between them which is smaller than the size spheres.
However, when the spheres are bigger in size, the
tetrahedral site becomes larger. In HCP and FCC, each
sphere is in contact with three spheres above and three
spheres below (see adjacent fig). Thus, there are two
tetrahedral sites associated with each sphere.
For example, in the FCC unit cell, the centres of the tetrahedral voids lie quarter - way and three - quarter
- way along the four nonparallel body diagonals of the cube (at a distance of 3a/4 form ever corner along
body diagonal). There are thus eight tetrahedral voids in the unit cell. As the effective number of atoms in the
unit cell is 4, this works out to a ratio 2 : 1 for the tetrahedral void to the atoms.
Octahedral void : An octahedral void is formed with three spheres on a close packed plane and three
more spheres on an adjacent close packed plane. Note that the three spheres of the adjacent plane are
positioned such that the centres of the three spheres are directly over the three triangular valleys surrounding
the central valley of the first plane, with no sphere over the central valley. The given figure is tilted view of the
octahedral arrangement, showing the square base with one sphere each on top and at the bottom.
For example, in the FCC unit cell, the centres of the octahedral voids fall at the body centre and the middle
1
of the 12 cube edges. the effective number of octahedral voids per unit cell is then 1 1 12 4.
4
As the effective number of atoms in the unit cell is 4, this work out to a ratio 1 : 1 for the octahedral void to
the atoms.
In general, if in a Close Packed crystal (CCP or HCP), there are N spheres (atoms or ions) in the packing,
then Numbe of Octahedral voids = N and Number Tetrahedral voids = 2N
1 1 5
No. of A atoms Left 4 4 2
8 2 2
corner
atoms centerfaceatoms
1 5
No. of B atoms Left 4 2 1 1
4 2
centeredgatoms centerbodyatoms
This simplest formula of crystal is AB
Illustration - 4 In a solid AB having rock salt structure, if all the atoms touching 1 body diagonal plane
are removed plane are removed (except at body centre), then the formula for the left unit cell is :
(A) A 7B 3 (B) A 5B 3 (C) A 5B 3 (D) A7/2B 5/2
SOLUTION : (D)
The number of atoms in a crystal which surrounds particular atom as its nearest neighbour atoms in its
neighbourhod is called co-ordination number.
Note : (i) For diatomic atoms, co-ordination no. of a cation is the no. of surrounding anions of vice versa.
(ii) In crystals with directional bonds, co-ordination number is lower than that of crystals with non-directional
bond such as metals and ionic compounds.
(b) Hexagonal Packing : The particles in every next row are placed in the depression between the
particles of the first row. The particles in the third row will be vertically aligned with those in the first
row. This type of packing gives a hexagonal pattern and is called Hexagonal Close Packing (HCP).
Note :(i) The second mode of packing (i.e., HCP) is more efficient as more space is occupied by the sphere in
this arrangement.
(ii) In Square Close Packing, a central sphere is in contact with four other spheres whereas in Hexagonal
Close Packing a central sphere is in contact with six other spheres.
(a) When the spheres of the second layer are placed on the spheres of the first layer and the spheres of
the third layer on the spheres of second layer and so on. In this form of packing, the spheres are
vertically aligned and the voids are also vertically overlapping. It results in an inefficient way of three
dimensional packing. This leads to simple cubic packing with a packing efficiency of 52% (It has been
discussed in section 14)
(b) When the second layer is place in such a way that its spheres find place in the a voids of the first
layer, then b voids will be left unoccupied since under this arrangement no sphere can be placed in
them. Similarly there are two types of voids in the second layer. When both layers are considered
together, we have two type of voids marked as voids c and voids d.
The voids c are ordinary voids which lies
above the spheres of the first layer whereas
voids d lie on the voids of the first layer and
hence are combination of two voids ; one of
the first layer and other of the second layer
with the vertex on one triangle upward and
the vertex of the other triangle downwards
which leads to an octahedral void.
Figure shows the type of voids when two layers are considered
Now there are two way to build up the third layer :
(i) When a third layer is placed over to second layer in such a way that the spheres cover the tetrahedral
or c voids, a three dimension closest packing is obtained where the spheres in every third of alternate
layer are vertically aligned (i.e., the third layer is directly above the first, the fourth above the second
layer and so on). Calling the first layer as layer A and second layer as layer B, the arrangement is
called ABAB..pattern or Hexagonal Closed Packing (HCP). Molybdenum, Magnesium and
Beryllium crystallise in HCP structure.
Figure shows Hexagonal Closed Packing Figure shows e is shared by sic unit cells
1 1
Effective number of atoms per HCP unit cell 12 2 1 3 6
6 2
Note : 11.51% of the total volume of the middle layer sphere extends
out of one side of the parallelepiped. Another 11.51% of
this sphere extends out of an adjacent face of the unit cell,
leaving 76.98% enclosed within the unit cell boundary. The
excluded portions are precisely matched by portions of two
other middle layer spheres extending from adjacent unit cells
into the first unit cell toward the center of the equilateral
triangle centered over the unoccupied hole in the bottom
layer [See figure (a) and (b)].
(ii) When the third layer is placed over the second layer in such a way that spheres cover the octahedral
of d voids, a layer different from layers A and B is produced. Let us call it as layer C. Continuing
further a packing is obtained where the spheres in every fourth layer will be vertically aligned. This
pattern of stacking spheres is called ABCABC..pattern or Cubic Close Packing (CCP). It is
similar to Face-Centred Cubic (FCC) packing.
Note : In both HCP and CCP the coordination number is 12 because a sphere is in contact with 6 spheres in its
own layer. It touches three spheres in the layer above and three in the layer below.
Illustration - 5 When over a 2 dimensional square packing same layers are kept in the way so that the
centres are aligned in all 3 dimensions, coordination number of each sphere is :
(A) 6 (B) 8 (C) 12 (D) 10
SOLUTION : (A)
The co-ordination number is 6. (4 atoms in the plane + 1 atom above + 1 atom below the particular atom).
Illustration - 6
In an FCC crystal, which of the following shaded
planes contains the given type of arrangement of atom ?
Total tetrahedral voids = 12 (represented by ' ' and ' ' ) out
of which 8 are completely inside ' ' and ' ' are shared by
other unit cells (each shared in 3 unit cells)
Total octahedral void = 6 (represented by ' ' ). All are completely inside.
Illustration - 8
The co-ordination number of fcc structure for a metal in 12, since
(A) each atom touches 4 others in same layer, 2 in layer above and 6 in layer below
(B) each atom touches 4 others in same layer, 4 in layer above and 4 in layer below
(C) each atom touches 6 others in same layer, 5 in layer above and 1 in layer below
(D) each atom touches 8 others in same layer, 2 in layer above and 2 in layer below
SOLUTION : (B)
Illustration - 9 Which of the following statements is correct for a two-dimensional hexagonal close-packed
layer ?
(A) Each sphere is surrounded by six spheres (B) Each sphere is surrounded by six voids
(C) Each sphere has three voids (D) Each void is surrounded by three spheres
SOLUTION : (ABD)
(C) Effective number of atoms in a hexagonal unit
cell
1
6 1 1 3
3
Effective no. of voids in a hexagonal unit cell = 6
Hence, each sphere has 2 voids
(A) Each sphere is surrounded by six spheres
(D) Each void is surrounded by 3 spheres
(B) Each sphere is surrounded by six voids
Illustration - 10 Calculate the c/a ratio for an ideally close packed HCP crystal.
SOLUTION :
TheABAtype of stacking represents the HCP structure joining the centres of the three neighbouring atoms of
the middle plane to the centres of the atoms of the top and the bottom planes results in two tetrahedral with a
common base. The top and bottom atoms are centred at two lattice points, one above the other on the two
hexagonal basal planes of the unit cell. So, the distance between them is the unit distance along the c-axis. The
distance between any two adjacent atoms of a plane is unit distance along the a-axis. Unit of c is equal to twice the
normal from the apex of a tetrahedron to its base. Unit of a is equal to the side of the tetrahedron.
c 2PT
=
a RS
RU = RS2 SU 2 = a 2 a 2 /4 = 3a/2
2 a
RT = RU =
3 3
PT = PR 2 RT 2 = a 2 a 2 /3 = a 2 / 3
a 2 3
= = 1.633
c 3
Illustration - 11
Tick the close packing arrangements in the following :
HCP, CCP and their combination (HCP + CCP) are the close packed arrangement with packing efficiency
= 74%
IN-CHAPTER EXERCISE-B
1. Sapphire is aluminium oxide. It crystallises with aluminium ions in two-thirds of octahedral holes in
a closest packed array of oxide ions. What is the formula of aluminium oxide ?
Na Cl
NaCl
4 units 4 units 4 units
Co-ordination no. of Na+ = 6 [Na+ is present in octahedral void formed by six Cl ions]
Co-ordination no. of Cl = 6 [Cl is present is octahedral void formed by six Na+ ions
using reversibility principle]
Cs Cl
CsCl
1 units 1 units 1 units
1 1
8 6 1 4 8
cell 8
2 Alternate tetrahedral
FCC unit cell
The carbon atom in tetrahedral voids touches its 4 surrounding atoms (nearest neighbours), so the co-
ordination no. is 4.
Note : Carbon atoms in the FCC lattice do not touch at all (But carbon atoms which are present in the
tetrahedral voids touch the surrounding 4 atoms. So, centre to centre distance between two carbon
3a
atoms is 2r = where a is the length of the unit cell and r is the radius of the carbon atom.
4
Solids which follow the structure of diamond are called Diamond cubic
Zinc blende (ZnS) is a member of diamond cubic family where sulphide (S2) ions form a FCC lattice
with zince (Zn2+) ions present in alternate tetrahedral voids i.e. 4 out of 8 tetrahedral voids are
unoccupied.
We have two tetrahedral voids per body diagonal out of which one is filled but in alternate fashion with
other boyd diagonls.
No. of S2 ions per ZnS unit cell = 4 [S2 being present at corners and face centres of the unit
cell]
No. of Zn2+ ions per ZnS unit cell = 4 [Zn2+ being present in 4 out of 8 tetrahedral voids of the
unit cell]
Ca 2F
CaF2
4 units 4 units 8 units
Co-ordination no. of Ca2+ = 8 [One Ca2+ supports 8 tetrahedral voids and all are filled with]
(v) Antifluorite (Na2O) type : It is just opposite to the fluorite structure where role of cations and
anions is interchanged. So, oxide (O2) ions form a FCC unit cell and sodium (Na+) ions are present
in all the tetrahedral voids
No. of oxide (O2) ions per FCC unit cell = 4
No. of (Na+) sodium ions per FCC unit cell = 8
2Na O2
Na 2O
4 units 8 units 4 units
Illustration - 12 a a a
Diamond has face-centred cubic lattice. There are two atoms at (0, 0, 0) and , ,
4 4 4
coordinate. The ratio of the carbon-carbon bond distance to the edge of the unit cell is :
3 1 1 1
(A) (B) (C) (D)
16 4 4 2
SOLUTION : (A)
a a a
Distance between (0, 0, 0) and , , 2r
4 4 4
3a 2r 3
2r where 2r = bond distance
4 a 16
Illustration - 13 Which of the following statements is (are) correct for the diamond structure ?
(A) Each atom has 4 nearest neighbours and 12 next-nearest neighbours
(B) It is relatively empty
(C) The maximum proportion of the available volume which may be filled by hard spheres is only 0.34
(D) The maximum proportion of the available volume which may be filled by hard spheres is only 0.46
SOLUTION : (ABC)
3a
Atom (carbon) lying in the tetrahedral voids touches the surrounding 4 atoms at a distance of
4
a
And the face centre atom has 12 next nearest neighbours at a distance of
2
4 3
8 R
3 3a R 3
The packing efficiency (P.E.) where 2R
a3 4 a 8
32 3 3 3
Hence P.E. is : 0.34
3 8 64 16
The ratio of the cation to anion radius rc / ra for this configuration is 0.155, which can be worked out from
the simple geometry (see Illustration- 14). The triangular arrangement in (i) is one of the limiting situations.
The radius ratio is said to be a critical value because for value of rc / ra smaller than 0.155, the central
cation will rattle in the hole and not touch all the three anions at the same time, as illustrated in (ii). This
violates condion (a) above and leads to instability. When the radius ratio is less than 0.155, then only way to
satisfy all three conditions is to reduce the number of anions to 2. For values of rc / ra slightly greater than
0.155, all the anions touch the central cation but do not touch one another, as shown in (iii). All three
condtions of stability are still satisfied. This situation will prevail till the radius ration increases to 0.225, the
next higher critical value corresponding to tetrahedral (four) coordination. At rc / ra 0.225, the four
surrounding anions touch one another and also the central cation. This configuration is the same as that
obtained by fitting the largest possible sphere in the tetrahedral void of a close packed structure, (See
Illustration- 15).
A ligancy of five does not satisfy all the three conditions for stable configuration because it is always possible
to have six anions as an alternative to any arrangement that contains five anions, without a change in the
radius ratio. The critical condition for octahedral (six) coordination occurs at rc / ra 0.414, which is the
same as the size of the octahedral void in a close packed structure. Ligancies of 7, 9, 10 and 11 are again
not permissible.
The radius ratio ranges in which different values of ligancy are obtained are summarized in the given table. At
the end of the table, the limiting case of rc / ra 1 is identified with configuration of close packing of equal
sized spheres.
SOLUTION :
The critical condition for triangular coordination is shown in the adjacent figure.
The three anions touch one another as well as the central
cation. From the simple geometry, we can write :
2
R r cos 30 r Rr R
3
r 2
1 0.155
R 3
SOLUTION :
The critical condition for tetrahedral co-ordination is shown in the adjacent figure. Than anions touch one
another as well as the central cation. From the simple geometry, we can write :
3 2
2 R and h Rr where h
4 3
3 2
2R R r
4 3
r 3
1 0.225
R 2
Note : The centre of tetrahedron is at distance of 3/4th of h from the apex. Also, height of regular tetrahedron is
2 / 3 times is side of the tetrahedron.
SOLUTION :
The critical condition for octahedral co-ordination
is shown in the adjacent figure. The anions touch
one another as well as the central. From the simple
geometry, we can write :
2r 2R cos 45 2R
r
2 1 0.414
R
SOLUTION :
The critical condition for cubic void shown in the
adjacent figure. The anions touch one another as well
as the central cation. From the simple geometry, we
can write :
a 2R and 3a 2R 2r
r
3 1 0.732
R
The ligancy rules outlined above are obeyed in a number of cases. for example, in the NaCl crystal, the
radio r / r 0.54, which lies between 0.414 and 0.732. As listed in the previous table, the predicated
Na Cl
ligancy is six. The octahedral geometry of six chlorine ions surrounding a central cation is experimentally
observed. In MgO, r /r 0.59 and again the octahedral coordination is observed. In CsCl,
Mg 2 O 2
r /r 0.73, it is difficult to predict whether a six fold or an eight fold coordination will occur. It
Cs Cl
so turns out that the eight coordination is observed. In this case, that is, every cesium cation is surrounded by
eight chlorine anions.
The Si O bond in silica as well as in silicates is about 50% ionic and 50% covalent. Here, the central silicon
cation is surrounded by four oxygen anions located at the corners of a regular tetrahedron. This arrangement
satisfies both the ligancy rules (as rc / ra 0.29, then tetrahedral coordination is predicted from the previous
table, as well as the orientation relationships of (sp3) bonds).
The stability criteria listed above for predicting the ligancy may not always be valid. If directional characteristics
of bonding persist to any significant degree, the considerations based on the radius ratio alone will not lead
to the correct prediction of ligancy. In the above-discussed example of Si O coordination, the radius ratio
criterion and the bond angle requirements happen to coincide. In ZnS, where the bond is more covalent than
ionic, the ligancy predicated from r /r 0.48 is octahedral. Yet the four-fold coordination
Zn 2 S2
characteristic of (sp3) bonding is what is observed.
In the formation of ionic crystals, the ligancy rules described above determine the local packing around a
cation. The long-range arrangement of ions in the crystal is dependent on the following factors :
(i) In the crystal, the overall electrical neutrality should be maintained, whatever be the net charge on a
local group of a cation and surrounding anions. For example, in NaCl, where a cation is surround by
six anions, the net charge on (NaCl6) is five. Evidently, this has to be neutralized in the long range
arrangement.
(ii) The ionic bond being nondirectional, the ions are packed as closely as possible in the crystal, consistent
with the local coordination.
When the cation charge is not more than two or at best three and when the radius ratio is in the range 0.414-
0.732, the crystal structure can be described as a FCC or HCP packing of anions with the cations occupying
all or part of the octahedral voids in the structure. The fraction of octahedral voids that are filled depends on
the number of cations to anions in the chemical formula. Thus, for the rock salt (NaCl) structure, adopted by
hundreds of binary ionic compounds, r / r 0.54, and the anion packing is FCC with all octahedral
Na Cl
voids filled with sodium cations. Recall that there is one octahedral void per sphere in a close packed array.
A unit cell of NaCl crystal is shown in fig. below, with the large chlorine ions occupying the corner and
facecentred cubic positions and the sodium ions in the octahedral voids. The octahedral positions are at the
body centre and the midpoints of the cube edges. Note that, unlike in the monoatomic FCC crystal, the
chlorine ions do not touch one another along the face diagonal. This is so because the radius ratio of 0.54 is
greater than the size of the octahedral void in a close pakced structure, which is 0.414. The FCC close
packing is opened up here to the extent necessary to accommodate the sodium cations in the octahedral
voids.
As the FCC positions and the octahedral void centre are interchangeable like the body centre and the body
corners in the BCC cell, the NaCl structure can also be described as two interpenetrating monoatomic
FCC cells, one corresponding to the anions and the other to the cations. The sum of the their radii, rc / ra
r r a / 2, where a is the lattice parameter..
Na Cl
When rc / ra is in the range 0.7312 1, the eight fold coordination is observed. CsCl with
r r 0.91 is a typical example of this structure. The cesium ions are at the body centre and the
Cs Cl
chlorine ions are at the body corners. The space lattice is simple cubic, with a basis of one cesium ion plus
one chlorine ion per lattice point.
As an example of an ionic crystal with more than two types of ions, consider the crystal structure of spinels.
Spinels are compounds with tow different cations A2+ and B3+ and oxygen as the anion, with general
formula, AB2O4. Here, the oxygen anions form the FCC packing, For every four oxygen anions, there are
four octahedral sites and eight tetrahedral sites. Out of these twelve, only three are needed to fill the cations
of the above formula. In the normal spinel structure, the A cations are in the tetrahedral voids and the B
cations are in the octahedral voids. Alternatively, half of the B cations can occupy the tetrahedral voids while
the remaining half of the B cations and all the A cations are randomly distributed in octahedral voids, resulting
in the inverse spinel structure. In both normal and inverse spinels, only half of the octahedral site and 1/8 of
the tetrahedral sites are filled.
Note : When B2O3 Fe 2O3 , we have a series of compound calls ferrites, where different cations can be present
in varying proportions. Ferrites have the inverse spinel structure.
4 3 4 3
1 r 2 r
P.E. 3 100 P.E. 3 100
3 3
a a
3a
Where 2r = a [a length of unit cell] Where 2r [a length of unit cell]
2
3 3
4 1 8 3 3
P.E. 100 100 52% P.E. 100 100 68%
3 2 6 3 4 8
3 3
16 1 32 3 3
P.E. 100 100 74% 100 100 34%
3 2 2 3 2
3 8 16
4 3
6
r
P.E. 3 100
3 2
6 a c
4
2 2
where c a and 2r a [a length of unit cell]
3
P.E. 100 74%
3 2
Note : If nothing is mentioned, we consider the limiting case i.e. anions-anions are also contact at the same
time when caton-anion contact is always present. So, we can always have cation-anion contact equation
but anion-anion contact equation is possible for limiting case only.
3a
Such that rA rB [a length of unit cell]
4
3a
Such that rA rB [a length of unit cell]
4
Note : Here radius ratio rules will changes. Now, lies in 0.225 0.414 as anion lies in tetrahedral void.
3a
Such that r r [a length of unit cell]
A B 4
DENSITY Section - 15
It is defined as the ratio of mass of the unit cell and volume of unit cell.
mass of atoms present in unit cell
Density
volume of unit cell
No.of atoms of each kind Molecular weight of each kind in a.m.u. 1.67 1027 kg
Density
volume of unit cell
Illustration - 18 Al crystallises in cubic shape unit cell and with edge length 405pm and density 2.7g/cc.
Predict the type of crystal lattice.
SOLUTION :
No.of atoms Molecular weight 1.67 1027 kg
Density
volume of unit cell
3 3 n 27 1.67 1027
2.7 10 kg / m n4
3
4.05 10
10
Illustration - 19 CdO has NaCl structure with density 8.27 g/cc. If the ionic radius of
O 2 is 1.24 A, determine ionic radius of Cd 2 .
SOLUTION :
8.27 103 kg / m3
4 128.41 1.67 1027
a 4.70 A
3
a
We have, Cd
2 r 2 r
O 2 a
r 1.24 2.35 r 1.11A
Cd 2 Cd 2
NOW ATTEMPT IN-CHAPTER EXERCISE-C BEFORE PROCEEDING AHEAD IN THIS EBOOK
Note 1 : (i) The above two defects are intrinsic defects, or thermodynamic defects.
(ii) AgBr is a compound in which both Schottky and Frenkel defects are found because AgBr is
highly ionic but there is a great difference in the size of Ag and Br .
Note 2 : (ii) The number (n) of Schottky defects present in an ionic crystal containing N ions at temperature T
E
is given by : n N exp where E is the energy required to create these n Schottky
2kT
defects and
(ii) Similarly, if Ni is the number of interstitial sites in an ionic crystal having N ions, the number n of
Frenkel defects is given by :
1
N 2 E
n exp where E is the energy required to create these n Frenkel defects.
Ni 2kT
(iii) It may be noted that number of Schottky & Frenkel defects increases exponentially with increase
in temperature.
(iv) In NaCl, there are approximately 106 Schottky pairs per cm3 at room temperature. In 1 cm3 ,
there are about 1022 ions and therefore there is one Schottky defect per 1016 ions.
Zn 2 1 O2 2e
ZnO
2
The excess Zn 2 ions thus formed get trapped into the vacant interstitial sites and the electrons
in the neighboring interstitial sites. It turns yellow when hot and white when cold.
Note : Crystals with either type of metal excess defect act as semiconductors.
Illustration - 20 If all the atoms touching 1 face plane are removed in a solid A B having rock salt type
structure, then the formula of the left compound and defect brought by this removal respectively is :
1 1
Atoms at the corners and face centre are B type atoms No. of B atom left 4 4 1 3
8 2
A atoms are present at body centre with probability (share) = 1 and at edge centres with probability (share)
1
4
1
Hence no. of A atoms left after removal will be 4 4 3
4
Hence 3 A type and 3 B type atoms left. So, the formula is AB.
(A) lowers the density of the KCl crystal (B) raises the density of the KCl crystal
(C) does not affect the denstiy fo the KCl crystal (D) increases the Frenckel defects of the KCl crystal
SOLUTION :
Once Ca 2 lets two K leave the crystal to maintain the electrical neutrality of the compound.
The Mass of two K is greater than the mass of C2, hence density decreases.
Properties of the solids depend mainly upon their structure and composition. Three main properties are
discussed below :
(a) Conductors
Solids through which electricity can flow to a large extent are called conductors. Depending upon the
type of charge carriers, the conductors are further classified as metallic and electrolytic conductors. In
metallic conductors, electrons are the charge carriers. In electrolytic conductors, ions are the charge
carries. Therefore electrolytic conductors conduct only when there are mobile ions i.e., in molten
state. However in solid stat they conduct electricity only to a small extent, which is due to the presence
of defect (hole, electrons etc). e.g. , NaCl, KCl.
(b) Insulators
The solids which almost do not allow the electricity to pass through them are called insulators. e.g.,
S,P.
(c) Semiconductors
The solids whose conductivity lives between metallic conductors and insulators are called
semiconductors. The electrical conductivity of semiconductors is due to the presence of impurities
and defects. Their conductivity increases with increase in temperature as the defects increase with the
increase in temperature.
The magnitude of the electrical conductivity strongly depends on the number of electrons available to
participate in the conductor process.
In metals, the atomic orbitals form molecular orbitals, which are so close in energy to each other as to
form a band. If conduction band is not completely full or it lies very close to a higher unoccupied band,
then electrons can flow easily under an electric field thereby showing conductivity.
In case of semiconductors, the energy gap between valence band and the conduction band is small
and hence some of the electrons may jump from valence band to conduction band and the result is
some conductivity.
In case of insulators, the difference of energy between valence band and conduction band is so
large that electron transition doesnt take place. Hence, no conductivity is shown. The in-between
region is called Forbidden zone.
The fundamental magnetic moment is the Bohr Magneton m B , which is equal to 9.27 1024 Am 2 .
For each electron in an atom, the spin magnetic moment is B (depending on the two possibilities of the
spin). The contribution of the orbital magnetic movement is equal to mi B where mi is the magnetic
quantum number of the electron. Materials can be classified depending on their response to external magnetic
field.
(a) Diamagnetic Materials : Substances which are weakly repelled by external magnetic fields. This
property is shown only by those substances which contain fully-filled orbitals i.e., no unpaired electrons
are present e.g, TiO 2 , NaCl.
(b) Paramagnetic Materials : Substances which are attracted by the magnetic field but lose their
magnetism in the absence of the magnetic field. This property is shown by those substances whose
atoms, ions or molecules contain unpaired electrons eg., O 2 , Cu 2
Note : Ferromagnetic, Antiferromagnetic and Ferrimagnetic solids transform to the paramagnetic stat at some
temperature due to randomisation of spins. Ferrimagnetic Fe3O 4 become paramagnetic at 850 K. It is also
observed that Ferromagnetic substances have a characteristic temperature above which no ferromagnetism
is observed. This is known as Curie temperature.
(b) Pyroelectricity :
Some polar crystals when heated produce a small current or pyroelectricity.
(c) Ferroelectricity :
In some piezoelectric crystals the dipoles are permanently lined up even in the absence of an electric
field. However, on applying electric field the direction polarization changes. e.g., BaTiO3 , Sodium
potassium tartrate (Rochelle Salt).
Note : All ferroelectric solids are piezoelectric but the reverse in not true.
(d) Anti-Ferroelectricity :
If there is no net dipole moment it is said to be an antiferroelectric crystal. This is because the dipoles
are alternately arranged. e.g., Lead zirconate (PbZrO3).
(e) Superconductivity :
When the electrical resistance of materials becomes almost zero, the material becomes superconductor.
The temperature at which the material shows superconductivity is called transition temperature. e.g.,
YBa 2 Cu 3 O7 at 90K.
IN-CHAPTER EXERCISE-D
1. Calcium crystallizes in a Face Centred Cubic unit with a = 0.556 nm. Calculate the density if
(a) it contains 0.1% Frenkel defects. (b) it contains 0.1% Schottky defects.
2. Sapphite is aluminium oxide. It crystallises with aluminium ions in two-thirds of octahedral holes in a
closest packed array of oxide ions. What is the formula of aluminium oxide ?
Example - 1 Spinel is an important class of oxides consisting of two types of metal ions with the oxide ions
arranged in CCP pattern. The normal spinel has 1/8 of the tetrahedral holes occupied by one type of metal
ion and 1/2 of the octahedral holes occupied by another type of metal ion. Such a spinel is formed by Zn 2+,
Al3+ and O2 with Zn2+ in the tetrahedral holes. If CCP arrangement of oxide ions remains undistorted in the
presence of all the cations, find the formula of spinel and fraction of the packing fraction of crystal :
SOLUTION :
No. of O2 ions = 4 r 3 r 2
2+
Now Zn is present in one of the tetrahedral where Al 0.414 , Zn 0.225 and
r 2 r 2
voids and two Al3+ are present in two out of O O
four octahedral voids for the electrical neutrality 2a 4r
O2
of the crystal.
[Limiting case as structure is not distorted]
So, the formula of spinel is : ZnAl2O4
Hence P.E. = 77%
4 4 4
2 r3 3 1 r 3 2 4 r 3 2
P.E. 3 Al 3 Zn 3 O
3
a
Example - 2 Assume an FCC unit cell cube (edge length a) with one of its
corners
at the origin of cartesian coordinates. Find :
(i) the coordinates of tetrahedral and octahedral voids nearest
and farthest to the origin.
(ii) find the distance between two succesive tetrahedral voids.
(iii) the distance between two successive octahedral voids.
SOLUTION :
(i) co-ordinates of tetrahedral void nearest to co-ordinates of octahedral void nearest to origin
origin
a a a
0, , 0 ; , 0 , 0 ; 0, 0,
a a a 2 2 2
, ,
4 4 4 co-ordinates of octahedral void farthest to origin
co-ordinates of tetrahedral void farthest a a a
, a , a ; a, , a ; a, a,
to origin 2 2 2
3a 3a 3a
, ,
4 4 4
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(ii) Distance between two successive tetrahedral (iii) Distance between two successive octahedral
voids voids = Distance between body centre and any
a
Distance between P a , a , a and edge centre of the FCC unit cell i.e.
4 4 4 2
3a a a a
Q , , i.e.
4 4 4 2
Example - 3 The number of Schottky defects (n) present in an ionic crystal containing N ions at tempera-
ture T is given by n = NeE/2KT, where E is the energy required to create n Schottky defects and K is Boltzmann
constant. If the mole fraction of Schottky defect in NaCl crystal at 2900 K is X (Given : H of Schottky defect
= 2 eV and K = 1.38 1023 JK1 , e = 1.608 1019 ), then calculate ln (X).
SOLUTION :
The number of schottky defects (n) is given as Mole fraction of defect is given as :
n = NeE/2KT . . . . (i) n n
N NA N e E/ 2KT
No. of moles of ions = X X
NA n N n e E/ 2KT 1
1
N NA NA N
No. of moles of schottky defects = [Using (i)]
NA
19
Substitute the value of E = 2 1.608 10 J
to get : nX ~ 4
Example - 4 Sulphide of cobalt metal has a cubic structure with four formula weights per unit cell. If
density is 4.269g/cc and edge length of unit cell is 6.93A, determine mass of sulphur required to produce 1.5
kg of this compound.
(Molecular weight of Co = 58.94 and S = 32 amu)
SOLUTION :
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Example - 5 FeO crystallizes in NaCl type of crystal lattice. The crystals however are always non-sto-
ichiometric and deficient in iron. Some cationic sites are vacant and some contain Fe3+ ions but the combina-
tion is such that structure is electrically neutral. The formula approximates to Fe0.95O.
(i) What is the ratio of Fe2+ to Fe3+ ion in the solid ? (ii) What percentage of cation sites is vacant ?
SOLUTION :
(i) The compound is Fe0.95O Fe95O100 Fe 2 85 17
Hence,
Let compound has x% of Fe2+ and Fe3 10 2
(95 x)% of Fe3+ such that
(ii) No. of Vacant sites = 100 95 = 5%
2x 3(95 x) 2 100 0 x = 85
[Structure is neutral]
Example - 6 What fraction of the Ca atoms lies on the surface of a cubic crystal that is 1.0cm in length,
if the radius of Ca atoms is 96pm and it crystallizes in Body Centered Cubic arrangement.
SOLUTION :
As Ca atoms crystallizes in body centred cubic, Surface area of one face of crystal = 104 m2
we have : Surface area of one face of unit cell = a2
4 96 No. of square faces visible at one face of crystal
3 a 4R a pm
3 104
= 2.03 1015
a = 221.7 pm 10 2
(2.217 10 )
Volume of unit cell
No. of atoms = 1 2.03 1015
3 12 3 3 30 3
= a (221.7 10 ) m 10.9 10 m
Volume of crystal = (102)3 = 106 m3
[ one atom per face of unit cell
106 1
No. of unit cells = 9.17 1022 4 1 ]
30
10.9 10 4
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Example - 7 Ar crystallizes in Face Centered Cubic arrangements and density of solid and liquid Ar is
1.59g/cc and 1.42g/cc respectively. Find the percentage of empty space in liquid Ar.
SOLUTION :
Density of solid Argon = 1.59 g/cc, 74 100
density of liquid Argon = 1.42 g/cc Volume of solid argon in crystal cc
100 1.59
Let the solid argon crystal be 100 gm
Volume of liquid argon in crystal is given as :
100
Volume of argon crystal (solid ) cc x 100 74 100
1.59 x = 66.08 %
100 1.42 100 1.59
Empty space = 33.92 %
Note : You could also have simply solved using P.E. = constant
density
Example - 8 Cadmium oxide crystallizes in NaCl type of crystal lattice. The compound is however
usually non-stoichiometric with approximate formula CdO0.95. The defect arises as some cationic positions
are occupied by neutral Cd atoms instead of Cd 2+ ions and equivalent numbers of anionic sites are vacant.
(Molecular weight of Cd = 112.41 amu)
(i) What percentage of anionic sites is vacant ?
(ii) What is the density of non-stoichiometric solid : (a = 470 pm.) ?
(iii) If the edge length of the unit cell is 470 pm, what would be the density of the perfect solid ?
SOLUTION :
(i) % of anionic sites vacant = 5 %
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Example - 9 When heated above 916C, iron changes its crystal structure from Body Centred Cubic to
Cubic Closed Packed structure. Assuming that the metallic radius of the atom does not change, calculate the
ratio of density of the Body Centered Cubic crystal to that of the Cubic Closed Packing crystal.
SOLUTION :
2 M 1.67 1027
Density of iron in BCC kg Also, 3a 4r
Volume of unit cell
2 M 1.67 1027
d BCC
3
4r
3
Density of iron in FCC
P.E.
Note : You could also have simply solved using = constant
density
Example - 10 The unit cell length of NaCl is observed to be 0.5627nm by X-ray diffraction studies. The
measured density of NaCl is 2.164 g/cc. Correlate the difference of observed and calculated density and
calculate the percentage of missing Na+ and Cl ions.(Molecular weight of NaCl compound = 58.5 amu)
SOLUTION :
kg / m3 2.193g / cc 2.164
4 x x 3.947
dobs < dcalc implies some of the sites are vacant 2.193
Hence, missing sites = 4 3.947 = 0.053
x 58.5 1.67 1027
d obs kg/m3 0.053
10 3 % of missing sites = 100 1.325%
(5.67 10 )
4
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Example - 11 In an atomic Face Centered Cubic, all the lattice positions are occupied by A and the body
centred octahedral hole is appropriately occupied by B, without disturbing the Face Centered Cubic of A.
Calculate packing fraction of this solid.
SOLUTION :
No. of A atoms = 4, No. of B atoms = 1 3 3 3
4
4rA 2
1 rA
4 3 4 Hence packing fraction=
4 rA 1 rB3 3 3
Packing fraction = 3 3
2 2 rA
3
a
3
2a 4rA and 2 rA rB a
12 2
4
2 1 0.75
rB
rA rB 2 rA
rA
2 1
Example - 12 A metallic element has simple cubic arrangement where edge length = 288 pm, density = 7.5
g cm3 . Find the number of atoms in 100g of the metal.
SOLUTION :
(Number of atoms ) (Molecular weight) 1.67 1027 kg
d
Volume of unit cell
g 100
No. of atoms = 6.023 1023 6.023 1023 5.6 1023
M 107.8
Example - 13 Find the concentration of cation vacancies in a lattice of NaCl which has been dopped with
103 mole % of SrCl2 .
SOLUTION :
103 mole % of Sr Cl2 103 moles of Sr Cl2 in Note that for Sr2+ to occupy the place of Na+
100 moles of NaCl 105 moles are present in the crystal, it has to remove two Na+ leaving
in 1 mole of NaCl Hence 105 moles of Sr2+ onehole
are present [to balance the charge].
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Sr 2 2 Cl ]
[Use stoichiometry : SrCl2
1mole 1mole 2moles = 105 (6.023 1023) = 6.023 1018
No. of atoms = (No. of moles) 6.023 1023 So, no. of cation vacancies = no. of Sr2+ present.
Example - 14 The molar volume of KCl and NaCl are 37.46 mL and 27.94 mL respectively. Find the ratio
of the unit cube edges of the two crystals. (Assume both have same packing efficiency)
SOLUTION :
volume of 6.023 1023 formula units of KCl Similarly volume of unit cell of NaCl crystal
= 37.46 ml 100 27.94
4 mL
vo lume of 4 fo rmula units of x NA
37.46
KCl 4 ml
NA volume of unit cell |KCl a3 37.46
KCl
volume of unit cell |NaCl a 3NaCl 27.94
volume occupied by KCl formula units
x 1/3
volume of unit cell a KCl 37.46
100 1.113
a NaCl 27.94
volume of unit cell of KCl crystal
100 37.46
= x N 4 mL
A
Example - 15 Calculate the void space in closest packing of n spheres of radius 1 unit, n spheres of radius
0.414 units and 2n spheres of radius 0.225 units.
SOLUTION :
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NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK
4 40 1.67 1027 kg
Density 1.554g / cc
(5.56 1010 )3 m3
(b) Density
0.1
4 4 40 1.67 1027 kg
100 1.55g / cc
=
10 3
3
5.56 10 m
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My Chapter Notes
Illustration - 1