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1 BONDING IN SOLIDS
1.1.1 INTRODUCTION
The most convenient basis for solid state theory is a classification scheme based on the
character of the interatomic bonding forces in various classes of crystalline materials.
According to this scheme of classification, all solids fall into one of the five general categories:
molecular, ionic, covalent, metallic and hydrogen bonded crystals. The distinction is not a
sharp one, because some may belong to more than one class.
It is a too fundamental fact that inert gases like helium, neon, argon, etc. exist in the
atomic form and not easily combine with other atoms to form new compounds because of
the magic number 2 in Helium and 8 in other cases. Interatomic force among the atoms in
a solid is one of the tools to classify the solids and then to study their physical properties.
1.1.2 FORCES BETWEEN ATOMS AND BOND ENERGY
The attractive electrostatic interaction between the electrons and positive charge of the
nuclei is totally responsible to group them and then for holding together. Gravitational
forces and magnetic forces are negligible compared with the said interaction. When two
atoms (or ions) come close to one another, there will be repulsion between negatively
charged electrons of both atoms. The repulsive force increases very rapidly as the distance
of separation decreases. However when the distance of separation is large, there is attraction
between positive nucleus and negative electrons. At some optimum distance (say r = r
o
),
the attractive and repulsive forces just balance and hence the resultant force becomes
UNIT 1
Bonding in Solids
&
Crystal Structures and Xray Diffraction
2 Applied Physics
zero. Hence the potential energy at this equilibrium spacing, r
o
becomes minimum. This
magnitude of minimum energy is called bond energy. It is usually expressed in kJ/kmol.
The value for primary bond ranges from 100 × 10
3
kJ/kmol to 1000 kJ/kmol and that of
secondary bond ranges from 1 × 10
3
to 60 × 10
3
kJ/kmol. The centre to centre distance of
two bonding atoms is called the bond length. The bond length increases on heating. The
bond energy and dissociation energy will be equal but opposite in sign. A crystal can only
be stable if its total energy (K.E + P.E) is lower than the total energy of the atoms or
molecules when they are free. The cohesive energy is defined as the difference of free
atom energy and crystal energy.
The variation of interatomic forces and potential energy vs distance of separation is
shown in Fig. 1.1. The general equation that represents the force between two atoms or
molecules or ions is
F =
N M
r
B
r
A
−
...(1.1.1)
A, B, M and N are constants; r is the interatomic distance.
Fig. 1.1 Interatomic forces and potential energy vs distance of separation.
From the above equation, one can arrive at the equation for the potential energy of
the system:
i.e., U(r) =
∫
dr F
=
C
r N
B
r M
A
N M
+
]
]
]
]
]
]
−
+
]
]
]
]
]
]
−
−
+ + 1 1
1
1
1
1
=
C
r
b
r
a
n m
+ + −
When U = 0 for r = ¥, C will be zero.
Thus
U(r) =
n m
r
b
r
a
+ −
...(1.1.2)
Bonding in Solids and Crystal Structures and Xray Diffraction 3
Here a, b, m and n are different constants. The first term of the above equation refers
to attraction and the second term repulsion. n is greater than m with n of the order of 9
and m = 2 for ionic structures. The forces of attraction result from interaction between
outer electrons of two atoms.
The forces of repulsion are from interpenetration of outer electronic shells. Only these
forces decide the nature of bonds in solids. The equilibrium distance r
0
may be determined
as follows:
0
r r
dr
dU
·
]
]
]
=
1
0
1
0
0
+ +
− ·
n m
r
bn
r
am
i.e.,
m n
r
−
0
=
¹ ¹
' '
¹ ¹
nb
ma
r
0
=
−
¹ ¹
' '
¹ ¹
1
n m
nb
ma
Also
n
r
0
=
]
]
]
ma
nb
r
m
0 ...(1.1.3)
1.1.3 COMPUTATION OF COHESIVE ENERGY
The energy will be minimum at r = r
0
i.e., [ ]
min
) (r U =
n m
r
b
r
a
0 0
+ −
Using
]
]
]
·
ma
nb
r r
m n
0 0
, we get
U
min
=
m m
nbr
mab
r
a
0 0
+ −
i.e., U
min
=
]
]
]
− −
n
m
r
a
m
1
0
...(1.1.4)
Conclusion: All stable arrangements of atoms in solids are such that the potential
energy is minimum. This is the only way of explaining the cohesion of atoms in solid
aggregates.
4 Applied Physics
1.1.4 IONIC BONDING
Ionic crystals are those compounds in which the valence electrons are completely transferred
from one atom to the other; the final result being a crystal that is composed of positively
and negatively charged ions. Atom whose outermost shell has only a few electrons given
up these electrons so that it is left with completely filled outermost shell. This process is
termed ionisation. On the other hand if the outermost shell is slightly short of eight electrons,
then the atom has a tendency to receive the electrons and become an ion.
An atom of sodium metal has one electron in its outermost shell and it can be easily
released with a sodium positive ion left with. This electron can be easily added to the
outermost shell of chlorine with seven electrons already. This chlorine atom becomes a
negative ion. Because of the mutual attraction between positive and negative ions, a bond
is developed between these two ions of opposite charges. The outermost electron of sodium
is removed by supplying 495 × 10
3
kJ/kmol (called first ionisation potential of sodium).
Na + E
1
® Na
+
+ e
1
This released electron will now move to occupy the outermost shell of chlorine (with
already seven electrons) and produce a negatively charged ion.
Cl + e
1
® Cl
The electron affinity of chlorine is 370 × 10
3
kJ/kmol. Thus net increase in potential
energy for transferring an electron from sodium to chlorine is 125 × 10
3
kJ/kmol. The
chemical reactions in the formation of NaCl at the equilibrium spacing are summarized
below:
Fig. 1.2 Schematic representation of the formation of ionic molecule of sodium chloride.
Na + Cl ® Na
+
+ Cl
® NaCl
Since chlorine exists as molecules, the chemical reaction must be written as
2Na + Cl
2
® 2Na
+
+ 2Cl
® 2NaCl
1.1.5 BOND ENERGY OF NaCl MOLECULE
NaCl is one of the best examples of ionic compound and let the sodium and chlorine atoms
be free at infinite distance of separation. The energy required to remove the outer electron
from the Na atom (ionisation energy of sodium atom), leaving it a Na
+
ion is about 5 eV; or
Na + 5 eV ® Na
+
+ e
Bonding in Solids and Crystal Structures and Xray Diffraction 5
Similarly when the removed electron from sodium atom is added to chlorine atom,
about 3.5 eV of energy (electron affinity of chlorine) is released.
Cl + e
® Cl
+ 3.5
Thus a net energy of (5.0 3.5) = 1.5 eV is spent in creating a positive sodium ion and
a negative chlorine ion at infinity.
i.e., Na + Cl + 1.5 eV ® Na
+
+ Cl
Now the electrostatic attraction between these ions brings them to the equilibrium
spacing r
o
= 0.24 nm and the energy released in the formation of NaCl molecule is called
the bond energy of the molecule and it is obtained as follows:
V =
) 10 24 . 0 )( 10 85 . 8 ( 4
) 10 6 . 1 (
4
9 12
2 19
0 0
2
− −
−
× × π
×
− ·
∈ π
−
r
e
= 2.56 ´ 0.0096 ´ 10
16
J
eV
10 6 . 1
10 0096 . 0 56 . 2
19
16
−
−
×
× ×
− ·
V = 6 eV ...(1.1.5)
Thus the energy released in the formation of NaCl molecule from the neutral Na and
Cl atoms is (5.0 3.5 6) = 4.5 eV.
Schematically,
Na
+
+ Cl
® Na + Cl + 4.5 eV ® NaCl
¬ 0.24 nm ®
This means that to dissociate one NaCl molecule 4.5 eV energy is required.
1.1.6 CALCULATION OF MADELUNG CONSTANT AND LATTICE ENERGY OF
IONIC CRYSTALS
The lattice energy of an ionic solid will differ from the bond energy of diatomic ionic molecules
since, in the former case there will be interactions between more atoms. The cohesive
energy of an ionic crystal is the energy that would be liberated by the formation of the
crystal from individual neutral atoms. The arrangement of Na
+
and Cl
ions in a sodium
chloride crystal is shown in Fig. 1.3.
Each sodium ion in sodium chloride is subject to the attractive potential due to 6
chlorine ions each at a distance r. Thus the attractive potential at the sodium ion by the
chlorine ion is
U
1
=
r
e
0
2
4
6
∈ π
−
The next nearest neighbours are 12 of the same kind of ions at a distance ( ) 2 r . Thus
U
2
=
( ) 2
4
12
0
2
r
e
∈ π
and so on.
6 Applied Physics
Fig. 1.3 Sodium chloride structure.
Thus the total potential energy is
U
coub
=
...
) 3 ( 4
8
) 2 ( 4
12
4
6
0
2
0
2
0
2
+
∈ π
−
∈ π
+
∈ π
−
r
e
r
e
r
e
=
¹
'
¹
¹
'
¹
+ − + −
∈ π
− ...
2
6
3
8
2
12
6
4
0
2
r
e
Let a =
¹
'
¹
¹
'
¹
+ − + − ...
2
6
3
8
2
12
6
All these relations are applicable only to univalent alkali halides (i.e., Z
1
= Z
2
= 1).
According to the scheme of Evjen, a = 1.75 which is close to the accurate value of
1.747558 obtained for NaCl structure by the Ewold method. This constant is called
Madelung constant.
Thus
U
coub
=
r
e
0
2
4 ∈ π
α −
The potential energy contribution of the shortrange repulsive forces can be expressed
as
U
rep
=
n
r
B
Bonding in Solids and Crystal Structures and Xray Diffraction 7
where B is a constant and U
rep
is positive which increases rapidly with decreasing
internuclear distance r. Thus the total potential energy U of each ion due to its interaction
with all other ions in the crystal therefore is
U(r) =
n
r
B
r
e
+
∈ π
α
−
0
2
4
...(1.1.6)
But at the equilibrium spacing r
0
, U is minimum and hence
0 ·
dr
dU
i.e.,
0
r r
dr
dU
·
]
]
]
=
0
4
1
0
2
0 0
2
· −
∈ π
α
+ n
r
nB
r
e
or
0 0
2
4 r
e
∈ π
α
= n
r
nB
0
i.e., B =
n
r e
n
0
1
0
2
4 ∈ π
α
−
...(1.1.7)
Substituting this value of B in equation (1.1.6) with r = r
0
, one gets
U
min
=
n
n
nr
r e
r
e
0 0
1
0
2
0 0
2
4 4 ∈ π
α
+
∈ π
α
−
−
=
0 0
2
0 0
2
4 4 ∈ π
α
+
∈ π
α
−
nr
e
r
e
or U
min
=
]
]
]
−
∈ π
α
−
n r
e 1
1
4
0 0
2
...(1.1.8)
Thus for one kmol of the crystal, the coulomb energy is
U
0
=
]
]
]
−
∈ π
α
−
n r
N e
A
1
1
4
0 0
2
...(1.1.9)
There are two other contributions to the cohesive energy of an ionic crystal that have
not been considered, (a) the van der Waals attraction between adjacent ions, which increases
the cohesive energy and (b) the zeropoint oscillations of their equilibrium positions which
decrease the cohesive energy. Both of these effects being very small in ionic crystals and
are usually neglected.
8 Applied Physics
1.1.7 THE COVALENT BOND
The existence of compounds such as H
2
, N
2
and O
2
as well as bonds in atomic crystals such
as diamond cannot be accounted for by ionic bonds because atoms of only one kind cannot
produce ions of opposite kind by transfer of electrons. The bonds that exist between atoms
of the same kind are called covalent bonds. In a covalent bond the electrons from the
outermost shell are shared by both the atoms. This may happen between two atoms of the
same type or different types. It may also be noted in this bond, the shared outer electrons
belong to both the atoms and not to this one or the other. Therefore, both the atoms are
neutral even after the formation of bond. It is due to this reason that solids formed by such
bond are usually called nonpolar substances.
The balance between the attractive and repulsive forces in hydrogen molecule occurs
at a separation of 0.074 nm. Hence some energy must be spent to break the covalent bond
in a hydrogen molecule into hydrogen atoms. About 4.5 eV energy is required to break one
bond between the hydrogen atoms. i.e.,
H
2
+ 4.5 eV ® H + H
The covalent bond between the two hydrogen atoms in a hydrogen molecule is
represented as:
H : H
It is desired to make clear that one electron has come from each atom, it is now indicated
as:
H
.
H ×
1.1.8 METALLIC BOND AND PHYSICAL PROPERTIES OF METALS
Metallic elements have low ionisation energies and hence, in this bonding, atoms of the
same element or different elements give their valence electrons to form an electron cloud
or say electron gas throughout the space occupied by the atoms. Having given up their
valence electrons, the atoms are in reality positive ions. These are held together by forces
that are similar to those of ionic bond in that they are primarily electrostatic, but are
between the ions and the electrons. Most of the atoms in metals have one or two valence
electrons.
These electrons are loosely held by their atoms and therefore can be easily released to
the common pool to form an electron cloud. The electrostatic interaction between the positive
ions and the electron gas holds the metal together. The high electrical and thermal
conductivities of metals follow from the ability of the free electrons to migrate through
their crystal lattices while all of the electrons in ionic and covalent crystals are bound to
particular atoms.
Unlike other crystals, metals may be deformed without fracture, because the electron
gas permits atoms to slide fast one another by acting as a lubricant. As we have seen
carbon can exist in the covalent form and so it is an extremely poor conductor. However, it
may also exist in an alternate form as graphite. In this case, bonds are formed in which
covalency is not fully achieved and these bonds can break and reform fairly as in metallic
Bonding in Solids and Crystal Structures and Xray Diffraction 9
Fig. 1.4 Bonding in metals.
bond. For this reason graphite is a conductor. If a p.d is applied between any two points in
a metal piece, the electron gas flows from negatively charged part to the positively charged
part, constituting electric current. The same free electrons are responsible for transferring
thermal energy from places of high temperature to places of low temperature due to their
mobility. This accounts for high thermal conductivity of metals. The diffuse nature of
electrons in the metallic materials make them opaque. The free electrons absorb light and
do not permit it to pass through. For the same reason the atomic planes can slide over each
other without causing bonds to rupture thus making the materials ductile.
Metals like sodium, copper and silver have these bonds. The transition metals such as
iron, nickel, tungsten,
have predominantly metallic bond with a significant fraction of
covalent bonds.
1.2 CRYSTAL STRUCTURES AND XRAY DIFFRACTION
1.2.1 INTRODUCTION
On the basis of structure, the solid state of matter can be put into two broad categories: the
crystalline and the noncrystalline (or amorphous). The distinction between the two does
not, however, depend on their external appearance or macroscopic form; instead, they are
distinguished from one another primarily by the degree of order exhibited by the
arrangement of the fundamental particles atoms, molecules or ions comprising them. In
crystalline solids, the atoms or ions (which may be compared with building blocks) are
stacked in a regular manner, just like the soldiers do on the parade ground, thus forming
a three dimensional pattern which may be obtained by a threedimensional repetition of a
building block or pattern unit. When the regularity of the pattern extends throughout a
10 Applied Physics
certain piece of solid, then it can be treated for many purposes a single crystal and would
be so called. However, most of the solids of technical interest such as metals, ceramics,
ionic salts, are not single crystals, but often consist of a large number of small crystal
sections (grains) of various shapes and sizes packed to one another in a quite irregular
way along the interfaces called the grain boundaries. In such materials the regularity or
periodicity is interrupted at the grain boundaries though the structure may be more stable.
These materials are called polycrystalline. The size of grain in which the structure is
periodic may vary from submicroscopic (many Angstroms) upwards and when it becomes
comparable to the size of pattern unit, one can no longer speak of crystals, since the essential
feature of a crystal is its periodicity of structure. One then speaks of amorphous substances.
Nature favours crystalline state for solids. This is because the energy of the ordered
atomic arrangement is lower than that of an irregular packing of atoms. However when
the atoms are not given an opportunity to arrange themselves properly, e.g., the temperature
of a liquid is dropped abruptly arresting the motion of atoms before they can rearrange
themselves, the amorphous material may be formed.
There are over 20000 crystalline substances in the crystal kingdom. Modern theory
of solids is founded on the science of crystallography, which is concerned with the
enumeration and classification of the actual structures of various crystalline substances.
Such enumeration and classification provide a natural starting point for mathematical
description of crystals. Thus in this chapter we begin our study of the physical properties
of crystalline solids by introducing the concept of crystal lattice and its application to the
classification of solids.
1.2.2 LANGUAGE OF CRYSTALS
Crystals are identified by their geometrical appearance; external surfaces are usually
plane faces. But how do atoms arrange themselves around each other in a crystal? A
crystal may be considered as a regular array of unitssmallest groupings that repeat
themselves in all directions in space. This repeating unit obeys the translation operation.
The collection of all translation operations constitutes the translation group. The translation
operation (vector)
T
H
is defined in terms of three translation vectors c b a
H
H
H
, , as follows:
c n b n a n T
H
H
H
H
3 2 1
+ + · ...(1.2.1)
where n
1
, n
2
, n
3
arbitrary integers. By letting ns assume all integral values, we can reach
an infinite, regular repeating array of units, that is, a crystal lattice. The translation
vectors c b a
H
H
H
, , are often called crystal axes and their directions are usually along the axes of
the primitive unit cell the smallest repeating unit of the crystal containing lattice points
only at its corners. When the operation,
T
H
is applied to any point r
H
in the material, the
resulting point ) (
3 2 1
c n b n a n r T r r r
H
H
H H
H
H
+ + + · + · ′ ′ must be identical in all respects with the
original point r. If
r
H
′
is not identical with
r
H
for any arbitrary choice of n
1
, n
2
, n
3
, the
vectors c b a
H
H
H
, , are not translation vectors. The geometry array of (lattice) points thus
generated constitutes the lattice. In order to convert this lattice into a crystal structure, we
must locate atoms, ions, group of atoms/ions, or molecules on the lattice points. The repeating
Bonding in Solids and Crystal Structures and Xray Diffraction 11
unit assemblyatom, ion, molecules, radical, etc. that is located at each lattice point is
called the basis. The crystal structure is thus given by two specifications: lattice + basis.
Lattice points are an array of points generated by the translation operation. The crystal is
generated by applying to the basis the translation group of operations for the type of
lattice under consideration.
Illustrations
Let us now consider the case of two dimensional array of points as shown in
Fig. 1.5. It is obvious from the figure that the environment about any two points is the
same; hence it represents a space lattice. In a mathematical form, the space lattice may be
defined as follows:
Fig. 1.5 Two dimensional array of points.
We choose any arbitrary point O as origin and consider the position vector
1
r
H
and
2
r
H
of any two lattice points by joining them to O. If the distance T
H
of the two vectors
1
r
H
and
2
r
H
satisfies the following relation,
b n a n T
H
H
H
2 1
+ ·
where n
1
, n
2
are integers and
a
H
and
b
H
are fundamental translation vectors characteristics
of the array, then the array of points is a two dimensional lattice. For three dimensional
lattice,
c n b n a n T
H
H
H
H
3 2 1
+ + ·
Hence it should be remembered that a crystal lattice refers to the geometry of a set of
points in space whereas the structure of the crystal refers to the actual ordering of its
constituent ions, atoms and molecules in the space.
The Basis and Crystal Structure
For lattice to represent a crystal structure, we associate every lattice point with one or
more atoms (i.e., a unit assembly of atoms or molecules identical in composition) called the
12 Applied Physics
basis or pattern. When the basis is repeated with correct periodicity in all directions, gives
the actual crystal. The crystal structure is real, while the lattice is imaginary.
Thus lattice + basis = crystal structure
Figure 1.6 shows the basis or pattern representing each lattice point. It is observed
from the figure that the basis consists of three different atoms. It can also be observed that
basis is identical in composition, arrangement and orientation. In crystals like aluminium
and sodium the basis is a single atom; in NaCl, KCl, etc. the basis is diatomic whereas in
crystals like CaF
2
the basis is triatomic.
Fig. 1.6 Space lattice, basis and crystal structure.
Unit Cell and Crystal Lattice
For discussing the unit cell, let us consider a two dimensional crystal in which the atoms
are arranged as in Fig. 1.7. If we consider a parallelogram such as ABCD with sides AB =
a and AD = b, then by rotating the parallelogram by any integral multiple of vector
a
H
and b
H
, the whole crystal lattice may be obtained. In this way the fundamental unit
ABCD is called a unit cell. Thus a unit cell is the smallest geometric figure, the repetition
of which gives the actual crystal structure.
Fig. 1.7 Two dimensional arrangement of atoms
Bonding in Solids and Crystal Structures and Xray Diffraction 13
The unit cell may also be defined as the fundamental elementary pattern of minimum
number of atoms, molecules or group of molecules which represent fully all the
characteristics of the crystal. It should be noted that the choice of a unit cell is not unique
but it can be constructed into a number of ways as A'B'C'D' or A"B"C"D" shown in
Fig. 1.7. The unit cell should be chosen in such a way that is conveys the symmetry of
crystal lattice and makes the mathematical calculations easier.
For a three dimensional case, the same procedure may be adopted. A three dimensional
unit cell is shown in Fig. 1.8(a).
Fig. 1.8(a) Three dimensional unit cell.
Fig. 1.8(b) Three dimensional unit cell.
The unit cell is a parallelepiped formed by the basis vectors c b a
H
H
H
, , as concurrent
edges and including angles a, b, g between b
H
and c
H
, c
H
and a
H
and a
H
and b
H
respectively as
shown in Fig. 1.8(b). Thus in general, a unit cell may be defined as that volume of a solid
from which the entire crystal may be constructed by translation repetition in three
dimensions. The entire lattice structure of a crystal is found to consist of identical blocks or
unit cells.
14 Applied Physics
1.2.3 CRYSTAL SYSTEMS AND BRAVAIS LATTICES
The crystalline structure is often referred to as latticed structure. A space lattice is an
infinite, three dimensional array of points in which every point has surroundings with
that of every other point as discussed earlier. The points with identical surroundings are
called lattice points. Since the regular pattern of atoms in a space lattice is regular, the
atomic arrangements must be described completely by specifying atom positions in some
repeating unit of the space lattice. This repeating unit of the space lattice is called a unit
cell. The unit cell may be regarded as the fundamental building block of a crystal, when
several of such unit cells are placed with common surfaces of contact result into a crystal.
The edges of unit cell must be vectors connecting any two lattice points.
The Bravais lattices describe the different arrangement in which lattice point can be
arranged in unit cells. Mathematicians have shown a long time ago that there are only
fourteen independent ways of arranging points in three dimensional space such that each
arrangement conforms to the definition of a space lattice. Thus there are fourteen Bravais
lattices. Each space lattice can be described with reference to its unit cell. Each unit cell
can be represented by three intersecting edges a, b, c and angles between a, b and c such
that the angle between b and c is a, that between c and a is b and that between a and b is
g. This configuration is shown in Fig. 1.9(a), seven different systems of crystals are obtained
by assigning different values to the edges a, b, c and angles a, b and g. For example the
simplest of all these, cubic crystal system is obtained when a = b = c and a = b = g = 90
o
,
such a system is shown in Fig. 1.9(b). Though not shown in the figure it may be remembered
that an atom will be sitting at each corner of the cube in Fig. 2.3.1(b).
Fig. 1.9 The axes and angles which describe a unit cell (b) A cubic unit cell.
When, only corners are occupied by atoms the system is known as primitive denoted
by P, some variations on this primitive system are also possible. For example, additional
atom may sit at the centre of all the faces, in which case the system is known as face
centred, denoted by F. If, however, the centres of only two opposite faces are occupied
additionally the system is known as base centred denoted by C. Yet another variation of
the crystal system is when an additional atom occupies the centre of the body of the unit
cell denoted by I. The seven crystal systems and fourteen Bravais lattices are described in
Table 1.1 and shown in Fig. 1.10.
Bonding in Solids and Crystal Structures and Xray Diffraction 15
Table 1.1 Crystal systems and Bravais lattices
Sl. System Axes Angles Bravais Lattice Number
No lattices symbol of lattices
in the system
1. Cube a = b = c a = b = g = 90° Simple, body P
centred, face I 3
centred F
2. Tetragonal a = b ¹ c a = b = g = 90° Simple, body P 2
centred I
3. Rhombohedral a = b = c a = b = g = 90° Simple P 1
(Trigonal)
4. Hexagonal a = b ¹ c a = b = 90° Simple P 1
and g = 120°
5. Orthorhombic a ¹ b ¹ c a = b = g = 90
o
Simple, P
(Orthogonal) base centred, C 4
body centred, I
face centred F
6. Monoclinic a ¹ b ¹ c a = b = 90
o
¹ g Simple, P 2
base centred C
7. Triclinic a ¹ b ¹ c a ¹ b ¹ g ¹ 90
o
Simple P 1
7 14
16 Applied Physics
Fig. 1.10 The fourteen Bravais lattices falling in the seven systems of crystals.
1.2.4 STRUCTURE OF METALLIC CRYSTALS
Many important properties of solids depend on their crystal structures. Fortunately,
relatively few of these need concern us: about threequarters of the elements (mostly metals
and a few semiconductors) used right from transmission lines to microinstruments in
spaceship are metals or semiconductors. These elements crystallize in one of the following
structures: face centred cubic (fcc), body centred cubic (bcc), hexagonal closepacked (hcp),
or diamond cubic crystal structure (dc). Though only one well known element polonium
crystallizes in the simple cubic structure, a minor study of this structure theoretically will
aid us to extend the frame work to calculate the packing fraction of other structures. The
simple study of this simple structure is now discussed.
1. Simple cubic structure (Primitive)
Fig. 1.11 Simple cubic structure.
The structure shown in the above figure teaches that eight atoms are arranged in a
regular cube, one atom at each corner. It is a cubic unit cell of parameter a. The
arrangement of atoms is repeated in all X, Y and Z directions. It can also be observed that
each corner atom is shared by 8 lattices. i.e., one corner of lattice atom shares effectively
1/8 atom to the unit cell under consideration. From the geometry of the cell it is clear that
side of the cube is equal to twice the radius of the atom. i.e., a = 2r. Thus
(1) volume of the unit cell is V = a
3
Bonding in Solids and Crystal Structures and Xray Diffraction 17
(2) number of atoms in a cell is, 1 8
8
1
· × · n
(3) nearest neighbours (or coordination number) = 6
(4) nearest neighbour distance 2r = a
(5) the lattice parameter a = 2 r
Thus the volume occupied by massive atoms in unit volume is called packing fraction,
and that is equal to
V
v
. [Here ν is the volume of all the atoms in a unit cell and it is
3
3
4
1 r π ×
i.e., PF =
3
3
3
3
) 2 (
3
4
3
4
1
r
r
a
r
V
v
π ·
π ×
·
=
52 . 0
6 8 3
4
·
π
·
×
π
% 52 or 52 . 0 · PF ...(1.2.2)
2. Body centred cubic lattice (bcc)
Iron is the most common metal used to fabricate iron curtain and to manufacture different
kinds of steel used in many nonbasic areas such as engineering and medicine crystallizes
in bcc structure. Hence it is absolutely essential to have a geometrical sketch of the unit
cell and an environmental study of the corner atoms and the atom sited at the body centre
in order to calculate its packing fraction.
Fig. 1.12 Body centred cubic.
Each corner atom in this structure is shared by eight cells an additional atom sits at
the body centre well within the unit cell touching the eight corner atoms along the body
diagonal and not along the edges as discussed in sc structure. The packing fraction of this
structure is computed using the following data and by having a look of Fig. 1.12.
2 2 2
) ( ) ( ) ( AF CA CF + ·
2 2 2 2
3 2 ) 4 ( a a a r · + ·
3
4
; 3 16
2 2
r
a a r · ·
18 Applied Physics
Thus
(1) nearest neighbour distance,
2
) 3 (
2
a
r ·
(2) the lattice parameter,
3
4r
a ·
(3) number of atoms in the unit cell,
,
`
.

× + · 8
8
1
1 2
(4) volume of all the atoms in the unit cell,
3
3
4
2 r v π × ·
(5) volume of unit cell,
3 3
64
3
3
r
a V · ·
(6) coordination number, CN = 8
Now
Density of packing or packing fraction,
3
3
3
3
3 64
3 3 8
3 3 / 64
3
8
.
r
r
r
r
V
v
F P
× ×
π ×
·
π
· ·
8
3
.
π
· F P = 0.68
% 68
8
3
. ·
π
· F P ...(1.2.3)
Chromium and barium are the other examples. Compared with sc structure, the
packing fraction of this structure is 16% more. Hence this bcc structure is called a closely
packed structure while the other one is loosely packed structure.
3. Face centred cubic lattice (fcc)
There are two forms of closest packing: face centred cubic (fcc) space lattice and hexagonal
close packed structure. Fig. 2.5.3 deals with fcc structure and helps us to find a way out to
compute the packing fraction following the general definitions made in the previous cases.
Here the lattice points (or atoms) are situated at all the eight corners as in the previous
two cases, but also at the centres of the six faces. The face centre atom shares with two
unit cells. Hence the number of atoms in a unit cell is
,
`
.

+ × 3 8
8
1
= 4. This lattice is also
known as a cubic F lattice. The atoms touch along the face diagonals. The packing fraction
is now calculated by the usual method.
(1) the lattice parameter,
2
4r
a ·
(2) nearest neighbour distance,
2
) 2 (
2
a
r ·
Bonding in Solids and Crystal Structures and Xray Diffraction 19
Fig. 1.13 Face centred cubic structure.
(3) number of atoms in the unit cell = 4
(4) volume of all the atoms in the unit cell,
3
3
4
4 r π × ·
= v
(5) volume of unit cell,
3
a V ·
(6) coordination number, CN = 12
Thus density of packing fraction,
]
]
]
]
·
]
]
]
]
π
· ·
3
3
) 4 (
2 2
3
16
.
r
r
V
v
F P
% 74 or 74 . 0
6
2
. ·
π
· F P ...(1.2.4)
copper, aluminium and lead are some examples of this structure.
Table 1.2: Comparison of cell properties of some crystal lattices
S. Diamond Simple Body Face Hexagonal
No. Properties cube cube centred centred close packed
(dc) (sc) cube cube structure
(bcc) (fcc) (hep)
1. Volume of unit a
3
a
3
a
3
a
3
) ( 3
2
3
2
c a
cell
2. Number of 8 1 2 4 6
atoms per cell
(Contd...)
20 Applied Physics
3. Number of atoms
3
8
a
3
1
a
3
2
a
3
4
a ) ( 3
4
2
c a
per unit volume
4. Number of 4 6 8 12 12
nearest
neighbours
5. Nearest
4
3 a
a
2
3 a
2
2 a
a
neighbour
distance (2r)
6. Atomic radius
8
3 a
2
a
4
3 a
4
2 a
2
a
7. Atomic packing 34 . 0
16
3
·
π
52 . 0
6
3
·
π
68 . 0
8
3
·
π
74 . 0
6
2
·
π
74 . 0
6
2
·
π
factor
8. Examples Germanium Polonium Sodium, Iron, Aluminium, Magnesium,
Silicon and Chromium Copper and Zinc and
Diamond Lead Cadmium
1.2.5 MILLER INDICES
Various properties of crystals, mainly mechanical properties are connected with the structure
of the crystal through the help of crystal directions and planes. In a crystal there exists
directions and planes which contain a large concentration of atoms. Xrays are easily
diffracted through planes containing large concentration of atoms. Miller evolved a method
to designate a set of parallel planes in a crystal by three numbers (h k l) known as Miller
indices.
Fig. 1.14 The (3 6 2) plane.
Bonding in Solids and Crystal Structures and Xray Diffraction 21
Consider the plane shown in Fig.2.7.1. The plane makes intercepts on all the axesat
3a units on the aaxis,
2
1
1
b units on the baxis and
2
1
4
c on the caxis. The Miller indices
of the plane are found by taking the reciprocals of the axial intercepts (ignoring the lattice
repeat units a, b, c):
3
1
,
2
1
1
1
,
2
1
4
1
, or
3
1
,
3
2
,
9
2
. Multiplying these three terms by 9, we get
the integers (3 6 2), which are called Miller indices of the plane. Negative intercepts are
written with a bar over them; thus ( ) 3 2 1 . If a plane is parallel to a given axis, then its
intercept is at infinity and its reciprocal is therefore zero; so a zero in the Miller indices of
a plane means that it must be parallel to that axis. For example, the (0 0 1) plane is
parallel to aand baxis and intercepts the caxis.
In short Miller indices are defined as the reciprocals of the intercepts made by the
plane, on the crystallographic axes when reduced to smallest numbers.
Crystal directions
The crystal directions are usually given in a square bracket like [ ]. It is easier to specify
crystal direction on a unit cell. In Fig. 1.15, three different directions are shown in the
orthorhombic lattice. The direction [1 1 1] is the line passing through the origin and point
P. The point P is at a unit cell distance from each axis. The direction [1 0 0] is the line
passing through origin and point Q. The point Q is at a distance 100 from X, Y, and Z axis.
Direction [101] is the line passing through origin and R. The point R is at distance of 101
form X, Y, and Z axes.
Fig. 1.15 Crystal directions.
22 Applied Physics
Conclusions
(i) All the parallel equidistant planes have the same Miller indices. Thus the Miller
indices define a set of parallel planes.
(ii) A plane parallel to one of the coordinate axes has intercept of infinity.
(iii) If the Miller indices of two planes have the same ratio; i.e., (8 4 4) or (4 2 2) or (2
1 1), then the planes are parallel to each other.
(iv) If (h k l) are the Miller indices of a plane, then the plane cuts the axes into h, k
and l equal segments.
(v) In specifying crystal direction, crystal axes are taken as base directions [3 3 3] or
[2 2 2] direction are identical to [1 1 1] direction. In such cases lowest combination
of integers i.e., [1 1 1] is used to specify direction.
Interplanar spacings
In a cubic system, the distance between two successive planes can be calculated by using
the relation
2 2 2
l k h
a
d
hkl
+ +
·
where h, k and l are the indices of the plane and a is the lattice constant. This important
equation may be obtained as follows:
(h k l) represents the Miller indices of the plane ABC. This plane belongs to a family
of planes whose Miller indices are (h k l ) because Miller indices represent a set of planes.
See Fig. 1.16.
Fig. 1.16 Interplannar spacing in cubic crystal.
Bonding in Solids and Crystal Structures and Xray Diffraction 23
Let β′ α′, and γ′ (different from interfacial angles a, b, and g ) be the angles between
coordinates axes XYZ respectively on ON'. and ON
Thus
k
a
OB
h
a
OA · · ,
and
l
a
OC ·
Also
OC
d
OB
d
OA
d
1 1 1
cos and cos , cos · γ′ · β′ · α′
...(1.2.5)
Again (ON)
2
= x
2
+ y
2
+ z
2
with ON = d
1
and
1 1
cos , cos
d
y
d
x
· β′ · α′
and
1
cos
d
z
· γ′
Thus ) cos cos (cos
2 2 2 2
1
2
1
γ′ + β′ + α′ · d d
2 / 1 2 2 2
1 1
] cos cos [cos γ′ + β′ + α′ · d d
In the Cartesian system of coordinates the sum of the squares of the direction cosines
is equal to 1.
Substituting this in eqn. (2.7.1), we get
1
2
1
2
1
2
1
·
]
]
]
+
]
]
]
+
]
]
]
OC
d
OB
d
OA
d
1
2
1
2
1
2
1
·
]
]
]
+
]
]
]
+
]
]
]
c
l d
b
k d
a
h d
For cubic system,
1 ) (
2 2 2
2
2
1
· + + l k h
a
d
) (
2 2 2
2
2
1
l k h
a
d
+ +
·
) (
2 2 2
1
l k h
a
d
+ +
·
Let ON' = d
2
be the perpendicular of the next plane PQR parallel to ABC. The intercepts
of the plane on these crystallographic axes are:
h
b
B O
h
a
A O
2
;
2
· ′ · ′
and
l
c
C O
2
· ′
(with OA' = OQ, OB' = OR and OC' = OP)
24 Applied Physics
and
α′ cos
=
C O
d
B O
d
A O
d
′
· γ′
′
· β′
′
2 2 2
cos and cos ,
...(1.2.6)
2
) ( N O ′ = γ′ + β′ + α′
2 2
2
2 2
2
2 2
2
cos cos cos d d d with ON' = d
2
But γ′ + β′ + α′
2 2 2
cos cos cos
= 1
Substituting this in Eqn. 1.2.6 and simplifying one gets
2
2
2
2
2
2
2 2 2
]
]
]
+
]
]
]
+
]
]
]
c
l d
b
k d
a
h d
= 1; for cubic system
1 ) (
) 2 (
2 2 2
2
2
2
· + + l k h
a
d
) (
2
2 2 2
2
l k h
a
d
+ +
·
Thus the interplanar distance between two adjacent planes of Miller indices (h k l)
in a cubic lattice is given by
) (
1 2
d d d − · =
2 2 2
l k h
a
+ +
...(1.2.7)
1.2.6 XRAY DIFFRACTION
A fine beam of Xrays fall on the single crystal. The crystal is rotated in such way that, at
some position of the crystal, Braggs condition is satisfied. By measuring the value of angle
q, the interplaner spacing can be calculated from Braggs equation.
(a) Laue method to study crystal structure
A single crystal is placed in the path of Xrays beam and the glancing angle q is kept
constant. Each set of plane will pick up various values of wavelengths; which can satisfy
Braggs law. Thus each set of plane will produce a spot which fulfils Braggs law. This
method is called Laue technique. Laue method is one of the principal methods used for the
analysis of crystal structure. A number of polychromatic Xrays strike at 90
º
on the plane
of a crystal under study. While passing through the crystal, the rays meet Braggs planes
having different interplaner spacings d. These different sets of planes make different
angles q with the direction of Xrays. Certain combinations q, and d satisfy the conditions
of Braggs law, with the resulting increase in intensity of diffracted Xrays.
Bonding in Solids and Crystal Structures and Xray Diffraction 25
Fig. 1.17 Xray diffraction (Laue method).
When primary rays pass though the crystal, they produce a black spot at point B on
the photographic plate PP. As different wave lengths are included in the primary
Xray, they will produce spots, which are less pronounced, around this central spot as
shown in Fig. 1.17. One of the planes considered as the plane for diffraction makes q with
the incident ray. Let A be the spot obtained on the photographic plate.
Thus θ 2 tan =
θ · 2 tan ; R AB
R
AB
By measuring AB and R, we can find the value of angle q for corresponding plane.
This method is usually used for single large size crystal.
(b) Powder crystal method (DebyeSherrer method)
This technique is used when single crystals of large size are not available. The crystalline
material is available either in the form of very small crystals or in powder form. In the
powder technic, a sample of material is ground into fine powder. The powder is then placed
in a capillary tube or pasted on thin wire or pressed and cemented into a thin spindle. This
powder specimen is placed at the centre around which a strip of circular photographic film
is positioned as shown in Fig. 1.18(a). A narrow beam of monochromatic Xrays is allowed
to strike the specimen (in capillary tube or wire or spindle) through a small hole. The
specimen (spindle, etc) is slowly revolved inside the specially constructed circular camera
called the powder camera. The Xray beam enters through hole a, passes through the
specimen and the unused part of beam leaves through hole b.
Let the incident rays make an angle q with a set of parallel crystal planes. There will
be reflection, if Bragg condition is satisfied. As there are a large number of randomly
oriented crystals in the powder, thus, there are many possible orientations of this set of
planes for same angle q. Consequently the reflected rays will not be in the form of parallel
26 Applied Physics
beam but they (reflected rays) will lie on the surface of a cone (like generators of a cone).
The apex of the cone is the point of contact of xrays with the specimen. For a fixed value
of n (say n = 1), there are so many combinations of d and q, that would satisfy Bragg
condition. For each combination, one cone of reflection will be there and hence so many
cones of reflection are emitted by the specimen. As the film is of narrow width only a part
of each reflected cone is recorded on the film which is positioned around the camera. The
recorded lines are in the form of pair of arcs as shown in Fig. 1.18(b).
Fig. 1.18 Xray diffraction (Powder technique) (b) photographic film (record).
The angle between the surface of cone i.e., reflected ray and exist of beam is 2q or we
can say that apex angle is 4q. In case the Bragg angle is 45
o
, the cone will take the form of
circle. This circle will interest the film strip at midpoints between the incident hole a and
exist hole b. When the Bragg angle is greater than 45
o
, back reflection takes place, the
reflected cones are formed toward incidence hole a.
The first pair of arc on each side of exit hole is due to smaller value of q. The other
pairs of arcs beyond this pair are due to larger value of q. The greater the value of q, the
farther will the arcs from the exist hole, the smaller will be the interplaner spacings
according to
θ
λ
·
sin 2
d . If the distance between a pair of arc is S, the value of S is related
with q as below:
S µ 4q
o
R 360 2 ∝ π
o o
R
S
90 360
4
2
θ
·
θ
·
π
Bonding in Solids and Crystal Structures and Xray Diffraction 27
o
R
S
90
2 θ π
·
The standard diameter of camera is 57.3 mm, then 2p R is equal to 57.3 × 3.14
= 180
o
S = 2q degree
The distance S is measured in mm. The half of this distance gives the magnitude of
angle q in degree. The value of q, along with other known data (n and l) is substituted in
Bragg equation and the interplaner spacing can be calculated. This Xray diffraction
technique is suitable for (i) identification of elements and compounds, because the powder
patterns are unique for each substance, (ii) determination of orientation of a single crystal
(iii) determination of structures of crystals of high symmetry (iv) estimation of grain size
of polycrystalline materials.
The experimental arrangement of powder crystal method is shown in Fig. 1.19.
Xrays from the tube are allowed to pass through filter F which absorbs all except one
wavelength of incident Xray beam of monochromatic one. This monochromatic beam is
now passed through two fine slits S
1
and S
2
cut in lead plates and then fall on powder
crystals C. A photo film is arranged around the inner surface of the camera as shown in
the figure.
Fig. 1.19 Experimental arrangement (Powder crystal method).
By measuring the intensities of arcs with the help of diffraction meter, the following
information can be obtained.
(a) By taking the photograph before and after heat treatment or cold working of a
crystal, the changes in the lattices can be studied.
(b) The dimensions of a unit cell and type of lattice can be determined for simple
cases.
(c) We can distinguish between crystalline and amorphous substances, as crystalline
substances produce lines (arcs) on photo film while amorphous substances do
not.
28 Applied Physics
SHORT QUESTIONS
1.1.1 Differentiate primary bonds and secondary bonds.
1.1.2 Discuss the interaction between the atoms in a diatomic molecule with suitable graphs.
(Anna. U., BE and Parttime BE, November 1993)
1.1.3 Why high external energy is required to melt ionic crystals?
1.1.4 Reaction between ionic compounds in solution state is high. Give reasons.
1.1.5* Show that the Madelung constant for a linear ionic solid having 2N ions of alternate
charge ± e is 2 ln 2. (Madras U., BE, November 1992).
1.1.6 Explain electric dipole. Give an example.
1.1.7 Explain the features of metallic bond with illustrations. (Anna. U., BE April 1999)
1.1.8 In crystals there is an attractive interaction of one kind or other which is quite
appreciable for nearest neighbours. Explain why they do not collapse?
1.1.9* If 440 × 10
3
kJ of energy is required to break the H H bonds in a kmol, compute
the energy required in eV to break one H H bond. (M.K. U., BE, April 1988)
1.1.10 Explain covalent bonds with two examples.
1.1.11 Describe the formation of hydrogen bonded crystals.
1.1.12 Explain van der Waals forces and molecular crystals. (Anna. U., BE, April 1990)
1.1.13 List out the different characteristics of hydrogen bonded crystals.
1.1.14 Experiments suggest that CCl
4
has no net dipole moment. Give the reasons.
1.1.15 The materials having metallic bonds are always opaque. Give one line answer.
1.1.16* Discuss the characteristics of hydrogen bonded crystals.
1.1.17 Explain electron affinity in bonding. (Anna. U., BE, April 1983)
1.1.18* What is meant by coordination number in solids?
1.1.19 What are the characteristic features of covalent bonded crystals?
(Anna. U., BE, May 1990)
1.1.20 Describe briefly metallic and van der Waals bonds. (Anna. U., BE, November 1989)
1.1.21 Compare and contrast the characteristics of ionic and covalent bonds.
(Anna. U., BE, November 1986)
1.1.22* Give reasons:
(i) magnesium oxide is bonded ionically
(ii) van der Waals bond is weak
(iii) liquid carbon tetrachloride cannot conduct electricity
(Question 1.1.22 has been taken from the B. Tech. question paper of Imperial
College of Science & Technology, London).
1.2.1 Define crystal structure, crystal lattice and Bravais space lattice.
1.2.2 Find the radius of the interstitial sphere that just fit into the void at the centre
between the body centred atoms of the bcc structure.
(Anna. U., BE, November 1995)
Bonding in Solids and Crystal Structures and Xray Diffraction 29
1.2.3 Distinguish crystalline and amorphous substances.
1.2.4 Explain the terms basis, lattice and crystal structure.
1.2.5* Distinguish space lattice and crystal structure.
1.2.6 Explain symmetry elements and symmetry operations in crystals.
(REC, Jaipur, December 2001)
1.2.7 Get the relation for the radius of the atom in terms of lattice parameter in
fcc structure. (Anna. U., BE/B. Tech, November 1996)
1.2.8 Describe the seven crystal systems.
1.2.9* Show that for a cubic lattice, the lattice constant a is given by
3 / 1
]
]
]
ρ
·
A
A
N
nM
a
where n is the number of atoms in a unit cell, M
A
is the atomic weight, N
A
is Avogadors
number and r is the density of the material (Anna. U., BE/B. Tech, November 1998)
1.2.10 How many atoms are there in the unit cell of diamond?
1.2.11 Distinguish primitive cell and unit cell.
1.2.12 List out the different kinds of symmetry elements and their total number in a cube.
(Anna. U., BE, May 1997)
1.2.13 Show that
c
a
ratio for an ideal hexagonal crystal is
8
3
(M. U., B. Tech/BE May 1984)
1.2.14 If the height of the unit cell of zinc (hcp) is 0.495 nm, compute the radius of zinc atom.
1.2.15 Explain rotationinversion axis in a cubical crystal.
1.2.16 Explain coordination number, nearest neighbour distance and packing factor with
the help of a highly crystalline solid. (M. U., B. Tech/BE, 1979)
1.2.17 What is meant by atomic radii in a crystal? How many atoms are there in the unit
cell of diamond?
1.2.18* Give the general explanation of closest packing with suitable figures.
1.2.19 What are Miller indices? Explain Burgers vectors. (Anna. U., BE/B.Tech., May 2002)
1.2.20 Silicon crystallizes in dc structure. If the lattice constant at 25
o
C is 0.5 nm. How
many unit cells will be there in a cubical crystal of side 0.5 cm.
1.2.21 What is Bravais lattice? Draw the planes (1 1 0) and (1 1 1) in a cubical unit cell.
(Anna. U., BE, April 2004)
1.2.22 The theoretical value of c/a ratio for zinc is 1.63. But the actual value of c/a for zinc in
hcp structure is 1.856. Explain.
1.2.23 Define atomic packing factor. What are Schottky defects.
(Anna. U., BE./B. Tech., May 1996).
1.2.24* What are Miller indices? How are they obtained? (JNTU, 2002)
1.2.25 Give the crystal structure of the following: (a) gold, (b) germanium, (c) barium,
(d) zinc. (JNTU; BE April 2001).
30 Applied Physics
1.2.26 What are Schottky defects? How are they formed?
(Anna. U., BE, November 2003)
1.2.27 Explain the terms i) basis, ii) space lattice, iii) unit cell. (JNTU, 2002)
1.2.28 Copper crystallizes in fcc structure. If the radius of the atom is r, find the distance
between the parallel planes (1 1 1) and (2 2 2).
(Bangalore University, May 2001)
1.2.29 Draw planes (1 1 0) and (1 1 1) in a cubic crystal.
1.2.30 Name different kinds of symmetry elements that are present in cubic crystal giving
the total number. (University of Groningen, Netherlands, U.G., 2002)
1.2.31 Discuss dc structure and get its packing factor. (Anna. U., BE, May 1990)
1.2.32 If 0.56 nm is the edge of the unit cell of NaCl, compute the shortest distance between
Na
+
ions. (IIT Mumbai, B. Tech. 1998)
1.2.33* Obtain the Miller indices of a plane which intercepts at a, b and c in fcc structure.
Also get the density of atoms in this plane. (M.K. University, B. Tech/BE, 1989)
1.2.34 Show that the Miller indices are the same for a family of crystallographic planes
which are parallel to each other. (Anna. U., BE/B. Tech., May 1989)
Answers to the starred questions
1.1.5* Let us take Na
+
at the point 0. The interaction between this and the nearest chlorine
ions at r
0
is
]
]
]
∈ π
− ·
∈ π
− +
∈ π
−
0 0
2
0 0
2
0 0
2
4
2
4 4 r
e
r
e
r
e
Similarly the repulsive energy due to the two positive ions at a distance 2r
0
is
0 0
2
2 4
2
r
e
∈ π
and that due to the next set of Na
+
ions is
0 0
2
3 4
2
r
e
∈ π
− . Thus the total energy due to
all the ions in the linear array is
]
]
]
,
`
.

+ − + −
∈ π
− ...
4
1
3
1
2
1
1 2
4
0 0
2
r
e
Bonding in Solids and Crystal Structures and Xray Diffraction 31
=
) 2 log 2 (
4
0 0
2
e
r
e
∈ π
−
i.e., a = 2 ln 2 = 1.38
1.1.9* The energy required to break 6.02 × 10
26
bonds is 440 × 10
6
joule. Hence the energy
required to break one H H bond is
19 26
6
10 6 . 1 10 02 . 6
10 440
−
× × ×
×
= 4.6 eV
E
d
= 4.6 eV
1.1.16* (i) they have the tendency to form groups of many molecules.
(ii) they have increased binding energy in comparison with similar molecules without
hydrogen bonded ones.
(iii) they have weak binding.
(iv) they have low electric conductivity and poor thermal conductivity.
(v) they are transparent.
1.1.18* It is the number of atoms around an atom or the number of atoms which are just in
the neighbourhood of atoms.
1.1.22* (i) because magnesium and oxygen are both divalent
2Mg + O
2
® Mg
++
+ 2O
® 2MgO
(ii) because it bonds only molecules together
(iii) because it does not contains C
4+
and Cl
ions
1.2.5* Space lattice is nothing but the geometry of a set of points in space whereas the
crystal structure denotes the real ordering or arrangement of the constitutent atoms
or ions.
1.2.9* Let M
A
, r and a be the atomic weight, density of the element and a is the lattice
parameter of the unit cell and n be the number of atoms in the unit cell. N
A
is
Avogadros number.
Thus
ρ
A
M
(molar volume) contains N
A
atom
a
3
will have
A
A
M
a N
3
ρ
atoms. This must be equal to the number of atoms in the unit
cell say n
i.e.,
]
]
]
]
ρ
A
A
M
a N
3
= ; n a
3
=
A
A
N
n M
ρ
a =
3 / 1
]
]
]
ρ
A
A
N
n M
Answer
32 Applied Physics
1.2.18* Closest packing is a way of arranging equidimensional objects such that the available
space is more efficiently filled. Under this each object will be in contact with maximum
number of like objects.
Fig. 2.18 Closest packing of spheres in twodimension and in threedimension.
1.2.24.* Let a plane cut the axes at 2a, 3b and c on x, y and z axes.
(a) Determine the coordinates of the intercepts made by the plane along the three
crystallographic axes (x, y, z).
x y z
2a 3b c
pq qb rc
(b) Express the intercepts as multiples of the unit cell dimensions, or lattice
parameters along the axes, i.e.,
a
a 2
b
b 3
c
c
2 3 1
Bonding in Solids and Crystal Structures and Xray Diffraction 33
(c) Determine the reciprocals of these numbers
2
1
3
1
1
(d) Reduce these reciprocals to the smallest set of integral numbers and enclose
them in brackets.
2
1
6 ×
3
1
6 ×
6 × 1
(3 2 6)
In general it is denoted by (h k l). Thus Miller indices may be defined as the
reciprocals of the intercepts made by the plane on the crystallographic axes when
reduced to smallest numbers.
1.2.33*
a a a
a
a
a
a
a
a
1 1 1
(1 1 1)
This plane is shown below.
The face diagonal is a × 2
Base calculation :
cos 60° =
2 a
AO
AO = ° α 60 cos 2
AO × 2 =
2
1
2 2 × × a
=
a 2
34 Applied Physics
The number of atoms in the plane is,
n =
2
2
1
1 3
6
1
· + ×
atoms
Height of the triangle,
cos 30° =
2
2
3
a
H
·
or H =
2 / 1
2
3
]
]
]
a
Area =
2 / 1
2
2
3
2
2
1
2
2
1
]
]
]
· × × × a H AO
=
2
2
3
a with a =
2
4r
Thus Area =
3 4
2
16
2
3
2
2
r
r
·
,
`
.

The planar density of (1 1 1) plane is
3 4
2
2
r
=
2
288 . 0
r
p.d =
2
288 . 0
r
Answer
REVIEW QUESTIONS
1.1.1 The potential energy of a diatomic molecule is given in terms of the interatomic
distance r by the equation
U(r) =
n m
r
b
r
a
+ −
Obtain the relation for the equilibrium spacing of the atoms and hence get the
expression for dissociation energy. (Anna. U., M.Sc., November 1983)
1.1.2 Describe the formation of NaCl lattice from neutral sodium chlorine atoms with
suitable figures and equations. (Anna. U., BE, November 1984)
1.1.3 What is meant by bond energy of NaCl molecule? Give the important steps to calculate
the lattice energy of ionic crystals and hence obtain the final expression for the
cohesive energy per kmol of the crystal.
Bonding in Solids and Crystal Structures and Xray Diffraction 35
1.1.4 Explain the difference between ionic and covalent types of binding. What do you
understand by Madelung constant? How madelung constant can be computed?
1.2.1 Explain the terms: lattice, basis, structure and unit cell. Discuss the seven systems
of crystals and the fourteen types of Bravais lattices with suitable figures.
1.2.2 What is meant by symmetry elements and symmetry operations? Discuss the various
types of symmetry elements in a cubic crystal. (Calicut. U., BE, May 1992)
1.2.3 Estimate the fraction of total volume occupied by atoms in body centred and face
centred cubic structures. Give two examples in each structure.
(M.U., BE,/B. Tech. November 1990)
1.2.4 Discuss the various symmetry elements associated with a crystal. Show that an actual
crystal cannot possess a fivefold rotational symmetry.
1.2.5 Compute the packing factor of bcc structure; why this structure is a closely packed
one and not a closest one?
1.2.6 Show that an ideal hexagonal close packed structure
a
C
is 1.663 and the density of
atomic packing equal to that of the facecentred cubic structure.
(JNTU, BE, May 2001)
1.2.7 Define Miller indices of a lattice plane and write the equation to a family of planes
represented by the indices (h k l). Show that for cubic crystal the distance d
h, k, l
between adjacent (h k l) planes is given in terms of the cubic edge a , by
2 2 2
l k h
a
d
hkl
+ +
· (M.K.U., P.G. April, 1999, Anna U., BE, May 1986)
1.2.8 Explain how Miller indices of a set of planes in a crystal are determined. Draw the
figures of a simple cubic crystal and indicate (1 0 0), (1 1 0) and (1 1 1) planes in it.
(Metallurgy division, University of Manchester, UK, B. Tech, April 1982, IIT Delhi, B.
Tech, May 1992).
1.2.9 Explain with neat sketches the different imperfections in a crystal. Calculate the
ratio of the number of vacancies in equilibrium at 300 K in aluminium to that produced
by rapid quenching from 800 K. Enthalpy of formation of vacancies in aluminium is
63 kJ/mol. (M.U., BE, November, 1992)
1.2.10 Define space lattice. Name the seven crystal systems and give the relation of lengths
of axes and the relation of angles between the axes of a unit cell in each type. Obtain
the coordination number for bcc and fcc lattices. (M.U., BE, April, 1994)
1.2.11 What are Miller indices? Draw neat diagrams to indicate Miller indices of some
important plane systems in a simple cubic crystal. Find the Miller indices of a crystal
plane that makes from some origin an intercept of a on the aaxis, 2b on the baxis
and 3c on the caxis. (JNTU, BE, May 2001, M.U., BE, April 1994)
1.2.12 Explain the dimensions of a unit cell. Derive an expression for the edge element of a
cubic crystal in terms of the properties of the crystal material. Zinc has hcp structure.
The radius of the atom is 0.153 nm. Compute the distance between the base and
middle plane containing the three atoms. (M.U., BE, May 2002)
36 Applied Physics
1.2.13 What are point, line and surface imperfections formed in solid materials? Illustrate
these imperfections with suitable sketches. (Anna.U., BE, April 1994)
1.2.14 Show that for bcc and fcc crystal structure, the lattice constants are given by
3
4r
a ·
and
2
4r
a · respectively where r is the atomic radius. Explain the following terms
used in crystallography: (1) primitive cell, (2) unit cell, (3) coordination number and
(4) relative density of packing. (Anna U., BE, May 1990)
1.2.15 Explain how xrays are used for determining the crystal structure. A sodium chloride
crystal of lattice constant 5.63 A
o
is used to measure the wavelength of xrays. The
diffraction angle is 5.2
o
for the d
111
spacing of the chlorine ions. What is the wavelength?
(M.U., BE, November 1992)
1.2.16 What is Bravais lattice? What are the different space lattices in the cubic system?
How many lattice points per unit cell are there in each of these lattices? Deduce an
expression for planes of the (h k l) type in the case of a cubic structure.
(Anna U., BE, April 1985)
1.2.17 Discuss in brief the type of bonding in a molecule of water. Sketch a unit cell of fcc
lattice. What are Miller indices? In a simple cubic lattice with lattice parameter a,
what is the interplaner distance between (1 1 1) type planes.
1.2.18 What is packing factor? Prove that the packing fraction of hcp is 0.74. Bring out the
differences between edge dislocation and screw dislocation.
(Anna U., BE, 2004 N.B: The first part of this question is not worded nicely)
1.2.19 Show that the atomic packing factor of fcc and hcp structures are the same. What are
Miller indices? Explain. How they are determined?
(Anna U., BE, December 2003. N.B: The sentence in the last part must be how they
are obtained?).
1.2.20 Explain primitive cell and unit cell. Prove that five fold rotation axis is not compatible
with a lattice. Classify the important types of crystal imperfections.
(Anna U., BE, December 2003, VTU, May 2003)
1.2.21 Explain the significance of Miller indices. Derive an expression for the number of
Schottky defects in equilibrium at a temperature T. The fraction of vacancy sites in
a metal is 1 × 10
10
at 500
o
C. What will be the fraction of vacancy sites at 1000
o
C?
(JNTU, B. Tech., 2002)
1.2.22 What are Miller indices? How are they obtained? Explain Schottky and Frenkel defects
with the help of suitable figures. (JNTU, B. Tech., 2000)
1.2.23 Calculate APF value for fcc structure. Copper has fcc structure and atomic weight of
copper is 63.54.
(Anna U., BE, May 1989. N.B: Some data are missing in the second part of the
question).
1.2.24 Draw the following planes in a cubical unit cell (0 1 1), (1 0 2), (1 3 2) and
(1 1 2). In an xray diffraction study, a radiation of wavelength. 1.71 A
o
was directed at
Bonding in Solids and Crystal Structures and Xray Diffraction 37
a cubic crystalline sample. It was found that the first two Bragg reflections occur at
angles of 30
o
, 35
o
17¢ respectively. Determine whether the crystal is bcc or fcc structure.
(VTU, BE, July 2004)
1.2.25 Discuss the crystal structure of diamond. Show that the packing fraction of fcc is
0.74. Discuss Braggs spectrometer and explain how it is used to verify the Braggs
law. (VTU, BE, July 2004)
1.2.26 Discuss Braggs law of xray diffraction. Describe the powder method to determine
crystal structure. (Anna U., BE, November 1995)
PROBLEMS AND SOLUTIONS
1.1.1 The force of attraction between ions of Na and Cl is 3.02 × 10
9
newton when the two
ions just touch each other. If the ionic radius of Na is 0.095 nm, what is the radius of
Cl
? (M.U., Five year BE 1980, AMIE, Winter 1999).
Solution:
F =
2
0
2
2 1 9
4
10 02 . 3
r
e Z Z
∈ π
· ×
−
In this case Z
1
= Z
2
= 1
Hence
9
10 02 . 3
−
×
=
2 12
2 19
10 85 . 8 4
) 10 6 . 1 (
r × × × π
×
−
−
i.e., r
2
=
9 12
38
10 02 . 3 10 85 . 8 14 . 3 4
10 56 . 2
− −
−
× × × × ×
×
= 0.0076 × 10
17
o r r = 0.276 nm
Thus
r =r(Na
+
) + r(Cl
)
Hence
r(Cl
) = 0.276 0.095
i.e., r(Cl
) = 0.181 nm Answer
1.1.2 Compute the net potential energy of a simple Na
+
Cl
ion pair. The equilibrium
distance between ions is 0.28 nm. The potential energy due to repulsion between
electrons is given by
8
r
U
r
β
· .
(Lincoln Laboratory, Massachusetts Institute of Technology, US, B. TechMid
semester, 1989).
38 Applied Physics
Solution:
If F
1
is the force of attraction between the ions, then
U
a
=
∫ ∫
∈ π
−
· dr
r
e Z Z
dr F
2
0
2
2 1
1
4
In the case of Na
+
and Cl
ions, Z
1
= 1, Z
2
= 1.
Hence U
a
=
C
r
e Z Z
+
∈ π
0
2
2 1
4
When r = ¥, U
a
= 0 and hence C = 0
U
a
=
r
e Z Z
0
2
2 1
4 ∈ π
U
a
=
r
e Z Z
0
2
2 1
4 ∈ π
r a
U U U + · =
8
0
2
2 1
4 r
b
r
e Z Z
+
∈ π
,
`
.

·
8
r
b
dr
d
F
r =
9
8
r
b
−
But F
a
= F
r
at the equilibrium position with F
a
= 3.02 × 10
9
N (taken from the
previous problem).
Thus F
r
= 3.02 × 10
9
=
9
8
r
b
−
b =
8
10 02 . 3
9 9 −
× × r
But r = r
0
= 0.28 × 10
9
metre
b =
8
10 02 . 3 ) 10 28 . 0 (
9 9 9 − −
× × ×
=
8
02 . 3 10 28 . 0
8
10 02 . 3 10 28 . 0
90 9 9 81 9
× ×
·
× × ×
− − −
b = 4 × 10
96
Thus U =
( )
8
0 0 0
2 19
4
10 6 . 1
) 1 ( 1
r
b
r
+
∈ π
×
× − ×
−
=
72 8
96
9 12
38
10 ) 28 . 0 (
10 4
) 10 28 . 0 ( 10 85 . 8 4
10 56 . 2
−
−
− −
−
×
×
+
× × × × π
× −
Bonding in Solids and Crystal Structures and Xray Diffraction 39
=
19 19
10 1 10 3 . 8
− −
× + × −
=
19
10 3 . 7
−
× − joule
U =
19
10 3 . 7
−
× − J Answer
1.1.3 If the repulsive energy is of the MottGurney form ]
]
]
ρ
− + ) (
exp
0
r r r
A
c a
where r
a
and r
c
are the basic radii of anions and cations respectively, then determine A
o
and r for
NaCl if the cohesive energy per ion pair is 6.61 eV and the interatomic separation is
0.282 nm. The ionisation energy and the basic radii of Na are 5.14 eV and 0.875 Å
respectively where as the electron affinity and the basic radii of Cl are 3.61 eV and
0.1475 nm respectively. (UPSC May 2000, B. Tech., IITMumbai, May 1992)
Solution:
Cohesive energy per ion pair is
U = I E C + R ...(1)
where I, E, C and R are ionisation energy of Na, electron affinity of Cl, coulomb
energy and repulsive respectively.
C =
r
e
0
4
75 . 1
∈ π
=
r
52 . 2
eV with r in nm
Now 6.61 = ]
]
]
ρ
− +
+ − −
) (
exp
52 . 2
) 61 . 3 14 . 5 (
0
r r r
A
r
c a
i.e., 6.61 = 1.53 ]
]
]
ρ
−
+
) 235 . 0 (
exp
52 . 2
0
r
A
r
...(2)
as
r
a
+ r
c
= (0.1475 + 0.0875) nm = 0.235 nm
0
r r
dr
dU
·
]
]
]
= ]
]
]
ρ
−
ρ
− + ·
) 235 . 0 (
exp
52 . 2
0 0
0 0
2
0
r A
r
with r
0
= 0.282 nm
or A
0
exp ]
]
]
ρ
) 047 . 0 (
= 31.69 r ...(3)
Substituting this in Eqn. (2), one gets
r = 0.025 nm Answer
Substituting r in Eqn. (3), we get
A
0
= 5.146 eV Answer
40 Applied Physics
1.1.4 Calculate the ratio of ionic radii for an atomic coordination number of three as
shown in figure. (V.U.T., Karnataka, BE May 2002)
Solution:
cos 30° =
866 . 0 ·
+ r R
R
R
r R +
=
154 . 1
866 . 0
1
·
R
r
+ 1
=
1 154 . 1 ; 154 . 1 − ·
R
r
R
r
= 0.154 Answer
1.1.5 Mr. Rudden used to add 500 cc of water to 500 cc of milk every time to prepare tea in
his shop. Can you suggest a method to estimate the number of water molecules
added each time?
Solution:
Yes sir. I can suggest a small formula to calculate the number of molecules present
in 500 cc of water.
If M and r are the molecular weight and density of water, then
ρ
M
is the molar
volume of water. Thus
cc
1
18
of water contains 6.02 ´ 10
23
water molecules;
Hence 500 cc of water will have
18
10 02 . 6 500
23
× ×
= 1.67 ´ 10
25
water molecules.
1.67 × 10
25
Answer
Bonding in Solids and Crystal Structures and Xray Diffraction 41
N.B: An apple in a day keeps the Doctor away; a cup of black tea mixed
with sufficient lemon juice twice a day keeps both the apple and the Doctor
away. Similarly pumping 5 × 10
25
(1.5 litre) molecules of water into the
stomach every day makes all the vital organs below the diaphragm to
function with pleasure and with least resistance.
1.1.6 The total energy per kmol of a crystal is given by the equation
U
r
=
]
]
]
]
α
−
r
e
r
B
N
n
A
2
What is the equilibrium nearestneighbour separation r
0
at which U(r
0
) in the above
equation is unchanged by replacing
n
r
B
by C exp (r/r)?
Solution:
B =
) / exp( ρ −r C r
n
with r = r
0
i.e., r
n
=
) / exp( ρ −r C
B
Differentiating this,
nr
n1
=
) / exp( ρ
ρ
r
C
B
Substituting for B
nr
n1
=
]
]
]
]
ρ
ρ
ρ ) / exp(
) / exp(
1
r
Cr
r
C
n
r
nr
n
=
ρ
n
r
with r = r
0
Thus r
0
= nr Answer
1.1.7 Calculate the value of the Madelung constant for the structure in the following figure.
All bond lengths are equal and all bond angles are 90
o
. Assume that there are no ions
other than those shown in figure and that the charges on the cations and anions are
+ 1 and 1.
(Department of Chemistry, B. Tech. programme 1997. The Open University, U.K.).
Solution:
There are seven ions in the structure; six cations and an anion. First we shall calculate
the contribution to the potential energy of interactions of the six cations with the
central anion. Each cation is distance r
o
from the central ion.
42 Applied Physics
Thus E
1
=
0 0
2
4
6
r
e
∈ π
−
Each cation also interacts with diametrically opposite cations (distance 2r
o
). There
are three such interactions, so
E
2
=
0 0
2
2 4
3
r
e
∈ π
+
Finally, E
3
is calculated from interactions between adjacent cations [distance
0
) 2 ( r ]
of which there are twelve.
Now
E
3
=
0 0
2
) 2 ( 4
12
r
e
∈ π
+
Thus
E = E
1
+ E
2
+ E
3
= ]
]
]
− −
∈ π
−
2
12
2
3
6
4
0 0
2
r
e
=
0 0
2
4 r
Ae
πε
with A = 6 1.5 8.5 = 3.99
A = 3.99 Answer
1.1.8 Calculate the cohesive energy of NaCl from the following data: r
0
= 0.281 nm,
A = 1.748, n = 9, ionisation energy of Na = 5.1 eV, electron affinity of Cl is 3.61 eV.
(JNTU, BE May 2002)
Solution:
The P.E. of an ion pair is V =
]
]
]
−
πε n
n
r
Ae 1
4
0 0
2
= 7.44 eV
Bonding in Solids and Crystal Structures and Xray Diffraction 43
To calculate the cohesive energy, we must add to this, the energy required to make
an ion pair from Na and Cl atoms. This energy is the difference between ionisation
energy of Na and electron affinity of Chlorine.
i.e.,
5.14 3.61 = 1.53 eV. Each atom therefore contributes half of 1.53 i.e., 0.77 eV to the
cohesive energy. Hence the cohesive energy of NaCl/atom is thus
E
c
= 3.72 + 0.77 = 2.95 eV.
E
c
= 2.95eV Answer
1.2.1 Explain allotropic forms of iron with ranges of temperatures. Whether any change in
volume is noticed when a metal exists in more than one form?
(Metallurgy division, University of Manchester, U.K, B. Tech., September 1982)
Solution:
When an element or a compound can exist in more than one crystalline forms at
different temperatures, the phenomenon is termed allotropy or isomorphism. The
most common example is that of iron which shows different allotropic forms at
different temperatures. Between 273 and 912
o
C iron is bcc crystal also called
a iron. Between 912 and 1394
o
C iron is in fcc form, also known as g iron. Between
1394
o
C and its melting point, iron is in bcc form called d iron. These are shown in
the following figure.
For bcc structure,
3
4r
a · with 2 atoms in an unit cell
For fcc structure,
2
4r
a · with 4 atoms in an unit cell
Volume of bcc unit cell per atom
V
b
=
3
3
3
3
158 . 6
2
3
4
2
r
r a
·
]
]
]
·
Volume of fcc unit cell per atom
V
f
=
3
3
3
3
658 . 5
2 2
16
2
4
4
1
4
r
r r a
· ·
]
]
]
·
44 Applied Physics
Now it is established that when bcc structure changes to fcc, there is a
reduction of volume for a given mass. the change of volume per atom is,
V ∆
= 6.158 r
3
5.657r
3
Answer
V ∆
= 0.501 r
3
1.2.2 Calculate the lattice constant of iron. Given: density of iron 7.86 kg/cm
3
; atomic
weight of iron 55.85 and Avogadros number 6.023 × 10
23
/mol. (Anna U. May 2004)
Solution:
This problem carries some errors. The density is 7.86 gm/cm
3
or 7860 kg/m
3
and it
is suggested to use 6.023 ´ 10
26
/kmol for Avogadros number instead of 6.023 ´ 10
23
/gmol as SI system is followed almost everywhere.
3
m
M
A
ρ
will contain N
A
atom.
Thus a
3
will have
A
A
M
a N
3
ρ
atom. This must be equal to n = 2
Thus n =
A
A
M
a N
3
ρ
or a =
3 / 1
]
]
]
ρ
A
A
N
n M
with
(i) r = 7860 kg/m
3
(ii) n = 2
(iii) M
A
= 55.85
(iv) N
A
= 6.02 × 10
26
/kmol
a =
9
3 / 1
26
10 287 . 0
10 02 . 6 7860
2 85 . 55
−
× ·
]
]
]
× ×
×
metre
a = 2.87 nm Answer
1.2.3 The lattice constant of aluminium (fcc) structure is 1.4 times the lattice constant of
chromium (bcc) structure. Compare the radii of the atoms of these metals. (Department
of Electronic and Electrical Engineering, Loughborough University of Technology,
U.K., November 1979).
Bonding in Solids and Crystal Structures and Xray Diffraction 45
Solution:
A
a =
2
4
A
r
a
C
=
3
4
C
r
C
A
a
a
=
2
3
4 . 1
C
A
r
r
·
or r
A
= C C
r r 14 . 1
732 . 1
414 . 1 4 . 1
·
×
r
A
= 1.14r
C
Answer
1.2.4 In a crystal whose primitives are 0.12 nm, 0.18 nm and 0.2 nm, a plane (2 3 1)' has an
intercept of 0.12 nm on the xaxis. Find the intercepts on the y and z axes.
(Bangalore U., BE, May 1982).
Solution:
Let p, q, r be the three intercepts, then
p : q : r =
1
2 . 0
:
3
18 . 0
:
2
12 . 0
Thus
q
p
=
1
18 . 0 2
3 12 . 0
·
×
×
i.e., q = p = 0.12nm as p = 0.12 nm
Similarly,
r
q
=
6 . 0
18 . 0
2 . 0 3
18 . 0
·
×
= 0.3
r =
nm
q
4 . 0
3 . 0
12 . 0
3 . 0
· ·
q = 0.12 nm, r = 0.4 nm Answer
1.2.5 The toycar of Mr. Ajay was heavily damaged; he threw all the parts except the
chase. It is of airon with bcc structure at 300 K and a rectangular plate with
dimensions 10 cm, 8 cm and 1 cm. Compute the number of unit cells in this specimen.
The nearest neighbour distance of this structure is 0.244 nm.
(University of Maryland, US, April 1982).
Solution:
a =
732 . 1
244 . 0 2
3
2 2
3
4 ×
·
×
·
r r
a = 0.282 nm
Volume considered 80 cm
3
46 Applied Physics
Thus
(0.282 × 10
7
)
3
cm
3
has one unit cell
80 cm
3
therefore will have
21 3
10 282 . 0
80
−
×
=
3
21
282 . 0
10 80×
= 3.57 × 10
24
cell
3.57 × 10
24
Answer
1.2.6 Aluminium has density of 2698 kg/m
3
. Its structure is fcc and atomic weight is 26.98.
Calculate
(a) How many atoms are contained in 1 m
3
of this metal?
(b) Get the size of the unit cube for aluminium.
(c) Calculate the atomic radius aluminium.
(d) Find the radius of the interstitial sphere that can just fit into the void at the body
centre of this fcc structure coordinated by the facial atoms.
(Anna. U. BE, November 1984, JNTU, BE, December 2001).
Solution:
(a)
2698
98 . 26
m
3
will contain 6.02 × 10
26
atom
1 m
3
may contain
98 . 26
10 02 . 6 2698
26
× ×
n = 6.02 × 10
28
Answer
(b) a =
3 / 1
]
]
]
ρ
A
A
N
n M
=
3 / 1
26
10 02 . 6 2698
4 98 . 26
]
]
]
× ×
×
= 0.406 × 10
9
m
a = 0.406 nm Answer
a = 0.406 nm
V = a
3
= 6.69 × 10
29
m
3
V = 6.69 × 10
29
m Answer
(c)
4
732 . 1
;
3
4
·
×
· ·
a
r
r
a
4
732 . 1 406 . 0 ×
= 0.176 nm
r = 0.176 nm Answer
(d) Let r be the radius of the atom and R be the radius of the sphere which can just
fit.
Bonding in Solids and Crystal Structures and Xray Diffraction 47
2(r + R) = a; r + R = a/2
or
r
r
r
a
R − · − ·
2 2
4
2
R =
176 . 0 414 . 0 414 . 0 ) 1 2 ( × · · − r r
R = 0.0729 nm Answer
1.2.7 The fraction of vacancy sites in a metal is 1 × 10
10
at 500
°
C. What will be the fraction
of vacancy sites at 1000
°
C? (Anna. U., M. Sc., September 1992)
Solution:
N
n
= ) / ( exp 10 1
10
T k E
B ν
−
− · ×
T k
E
B
ν
= 10ln10
E
v
= 773 × 10 × 2.3031× k
B
1
1
N
n
= exp
,
`
.

×
× ×
−
1273
3031 . 2 7730
B
B
k
k
1
1
N
n
=
7
10 44 . 8
−
×
Answer
1.2.8 NaCl has an fcc structure. The density of NaCl = 2.18 gm/cm
3
. Calculate the distance
between two adjacent cations. Given: molecular weight of NaCl is 58.5.
(University of Minnesota, US, MidSemester B. Tech., 1994)
Solution:
Mass of one molecule
23
10 02 . 6
5 . 58
×
= 9.708 × 10
23
gm
ρ =
1
m n
V
M ×
·
with V = 1
48 Applied Physics
Hence the number of molecules in 1 cm
3
of NaCl is
n =
23
10 708 . 9
18 . 2
molecule one of mass
−
×
·
ρ
i.e., n = 22.46 × 10
21
molecules/cc
Hence number of ions in one cm
3
= 2 × 22.46 × 10
21
= 44.92 × 10
21
One unit cell contains 8 ions; therefore number of unit cells in one cm
3
is
8
10 92 . 44
21
×
=
21
10 62 . 5 ×
i.e.,
1 cm
3
contains 5.62 × 10
21
unit cell
a
3
will contain
1
10 62 . 5
3 21
a × ×
= 1 unit cell
or
3
a
=
21
10 62 . 5
1
×
= 0.178 × 10
21
or a = 5.62 × 10
8
cm
Cationcation distance is the face diagonal of the primitive cell
2
D
=
2 2 2
2
2 2
a a a
·
,
`
.

+
,
`
.

D
=
8
8
10 98 . 3
414 . 1
10 626 . 5
2
−
−
× ·
×
·
a
cm
or D = 0.398 nm Answer
1.2.9 A diffraction pattern of a cubic crystal of lattica parameter a = 0.316 nm is obtained
with a monochromatic xray beam of wavelength 0.154 nm. The first four lines on
this pattern were observed to have the following values:
Line: 1 2 3 4
q° 20.3 29.2 36.7 43.6
Determine the interplanar spacings and Miller indices of the reflecting planes.
Solution :
d =
d
λ
· θ
θ
λ
sin ;
sin
Bonding in Solids and Crystal Structures and Xray Diffraction 49
Line
θ θ sin
d (nm)
2 2 2
2
2
l k h
d
a
+ + ·
1 20.3 0.3460 0.2240 2
2 29.2 0.4886 0.1570 4
3 36.7 0.5980 0.1290 6
4 43.0 0.6900 0.1150 8
For determining (h, k, l) one has to resort to trial and error method.
h
2
+ k
2
+ l
2
= 2 = 1
2
+ 1
2
+ 0; h k l = ( 1 1 0 )
h
2
+ k
2
+ l
2
= 4 = 2
2
+ 0 + 0; h k l = ( 2 0 0 )
h
2
+ k
2
+ l
2
= 6 = 2
2
+ 1
2
+ 1
2
; h k l = ( 2 1 1 )
h
2
+ k
2
+ l
2
= 8 = 2
2
+ 2
2
+ 0; h k l = ( 2 2 0 )
EXERCISE
1.1 The potential energy of a diatomic molecule is given in terms of the interatomic
density r by the expression
10 2
) (
r
b
r
a
r U + − ·
. Calculate the equilibrium spacing of
the two atoms and the dissociation energy. Given: a = 1.44 × 10
39
J m
2
and
b = 2.19 × 10
115
J m
10
. (Ans: 0.047 nm, 4.33 × 10
2
eV)
M.K. U., BE May 1990)
1.2 How many kgatom of potassium will be required to treat with 709.1 kg of chlorine to
form KCl? (Ans: 20 kgatom)
1.3 (a) How much energy is required to form a Li
+
and Br
ion pair from a pair of Li and
Br pair of atoms?
(b) What must be the separation between a Li
+
and Br
ion pair so that their total
energy is to be zero. Given: the ionisation energy of Li = 5.4 eV and electron
affinity of Br = 3.36 eV. (Ans: 2.04 eV, 0.71 nm)
(Anna. U. Parttime BE, May 1992).
1.4 The ionic radii of Cs and Cl are 0.165 nm and 1.81 nm and their atomic weights are
133 and 35.5 respectively. Calculate the density of CsCl. (JNTU May 1997).
(Ans: 4.37 × 10
3
kg/m
3
)
1.5 Assuming an overlap interaction between nearest neighbours of the type
f (r) = B exp( r/r) where B and r are constants, calculate the equilibrium spacing r
o
in terms of B and r. (Ans: r ln B)
(IIT Madras, BE May 1990)
50 Applied Physics
1.2.1 Calculate the atomic density (i.e., the number of atoms per unit area of a lattice
plane) in (1 0 0) and (1 1 0) planes of a bcc crystal having a as its lattice constant.
(AMIE, September 1988) (Ans: 1/a
2
,
2
/ 2 a )
1.2.2 How is the distance between two planes of same indices calculated? Calculate the
ratio of the distances of the planes with Miller indices (1 1 1) and that with Miller
indices (1 0 2) in lead crystallizes in fcc structure. Given radius of lead atom 0.174
nm. (Anna U., B.E. November 1992) (Ans: d
1
/d
2
= 1.3)
1.2.3 Magnesium has hcp structure. The radius of magnesium atom is 0.1605 nm. Calculate
the volume of unit cell of magnesium. (Ans: 1.4 × 10
28
m
3
)
1.2.4 Miss. Mithila a seventh standard student geometrically prepared a cube of common
salt as her project work in the junior school level. When it was shown to me I found
that it is a cube of NaCl with 1 cm edge. Compute the number of sodium ions and the
number of unit cells if the lattice constant is 0.56 nm. (Ans: 22.8 × 10
21
, 5.7×10
21
)
1.2.5 Copper has fcc structure and its atomic radius is 0.128 nm. Calculate the density of
copper if its atomic weight is 63.5. (Anna U., B.E., May 1989 and JNTU June 2004)
(Ans: 8.9 × 10
3
kg/m
3
)
1.2.6 Given the following data, determine whether a gaseous molecule A
+
B
will be stable
with respect to the separated A and B gaseous atoms:
First ionisation energy of A = 500 kJ/mol
Electron affinity for B atom = 335 kJ/mol
Interionic separation = 0.3 nm (Ans: 297 kJ/mol)
1.2.7 The lattice constant of the unit cell of a iron is 0.287 nm. Find the number of atoms/
mm
2
of the planes (1 1 0) and (1 1 1). airon has bcc structure.
(The Open University, UK).
(Ans: 1.72 × 10
13
, 2.11 × 10
13
)
1.2.8 Calculate the ratio of the number of vacancies in equilibrium at 300 K in aluminium
to that produced by rapid quenching at 800 K. Enthalpy of formation of vacancies in
aluminium is 68 kJ/mol. (M.U., BE, November 1992).
(Ans: 3.75 × 10
8
)
1.2.9 A gold smith used to prepare samples by adding 20 cc of copper in 80 cc of pure gold
every time for making ornaments. Once he had a wire of 200 cm with a uniform
diameter 0.5 cm prepared as per the above ratio. Find out the number of unit cells in
copper that is added to draw the wire. Also compute the number of copper atoms
present. Given : Copper takes fcc structure with a lattice constant of 0.36 nm.
(GATE 1995)
(Ans: 1.7×10
23
m, 6.8×10
23
)
2
Applied Physics
zero. Hence the potential energy at this equilibrium spacing, ro becomes minimum. This magnitude of minimum energy is called bond energy. It is usually expressed in kJ/kmol. The value for primary bond ranges from 100 × 103 kJ/kmol to 1000 kJ/kmol and that of secondary bond ranges from 1 × 103 to 60 × 103 kJ/kmol. The centre to centre distance of two bonding atoms is called the bond length. The bond length increases on heating. The bond energy and dissociation energy will be equal but opposite in sign. A crystal can only be stable if its total energy (K.E + P.E) is lower than the total energy of the atoms or molecules when they are free. The cohesive energy is defined as the difference of free atom energy and crystal energy. The variation of interatomic forces and potential energy vs distance of separation is shown in Fig. 1.1. The general equation that represents the force between two atoms or molecules or ions is F=
A B − N M r r
...(1.1.1)
A, B, M and N are constants; r is the interatomic distance.
Fig. 1.1 Interatomic forces and potential energy vs distance of separation.
From the above equation, one can arrive at the equation for the potential energy of the system: i.e., U(r) =
∫ F dr = − M − 1 r A 1 B 1 + N +1 + C M +1 N − 1 r
a b + n +C m r r When U = 0 for r = ¥, C will be zero. Thus a b U(r) = − m + n r r
= −
...(1.1.2)
Bonding in Solids and Crystal Structures and Xray Diffraction
3
Here a, b, m and n are different constants. The first term of the above equation refers to attraction and the second term repulsion. n is greater than m with n of the order of 9 and m = 2 for ionic structures. The forces of attraction result from interaction between outer electrons of two atoms. The forces of repulsion are from interpenetration of outer electronic shells. Only these forces decide the nature of bonds in solids. The equilibrium distance r0 may be determined as follows:
dU am bn dr = 0 = m+1 − n +1 r =r0 r0 r0
i.e.,
nb n r0 −m = ma
nb n −m r0 = ma
Also
m nb r0n = r0 ma
1
...(1.1.3)
1.1.3 COMPUTATION OF COHESIVE ENERGY
The energy will be minimum at r = r0 i.e.,
a b + n m r0 r0
[U (r )]min
= −
m nb Using r0n = r0 , we get ma
Umin = −
a
m r0
+
mab
m nbr0
i.e.,
Umin = −
a m r0
m 1 − n
...(1.1.4)
Conclusion: All stable arrangements of atoms in solids are such that the potential energy is minimum. This is the only way of explaining the cohesion of atoms in solid aggregates.
4
Applied Physics
1.1.4 IONIC BONDING
Ionic crystals are those compounds in which the valence electrons are completely transferred from one atom to the other; the final result being a crystal that is composed of positively and negatively charged ions. Atom whose outermost shell has only a few electrons given up these electrons so that it is left with completely filled outermost shell. This process is termed ionisation. On the other hand if the outermost shell is slightly short of eight electrons, then the atom has a tendency to receive the electrons and become an ion. An atom of sodium metal has one electron in its outermost shell and it can be easily released with a sodium positive ion left with. This electron can be easily added to the outermost shell of chlorine with seven electrons already. This chlorine atom becomes a negative ion. Because of the mutual attraction between positive and negative ions, a bond is developed between these two ions of opposite charges. The outermost electron of sodium is removed by supplying 495 × 103 kJ/kmol (called first ionisation potential of sodium). Na + E1 ® Na+ + e1 This released electron will now move to occupy the outermost shell of chlorine (with already seven electrons) and produce a negatively charged ion. Cl + e1 ® Cl The electron affinity of chlorine is 370 × 103 kJ/kmol. Thus net increase in potential energy for transferring an electron from sodium to chlorine is 125 × 103 kJ/kmol. The chemical reactions in the formation of NaCl at the equilibrium spacing are summarized below:
Fig. 1.2 Schematic representation of the formation of ionic molecule of sodium chloride.
Na + Cl ® Na+ + Cl ® NaCl Since chlorine exists as molecules, the chemical reaction must be written as 2Na + Cl2 ® 2Na+ + 2Cl ® 2NaCl
1.1.5 BOND ENERGY OF NaCl MOLECULE
NaCl is one of the best examples of ionic compound and let the sodium and chlorine atoms be free at infinite distance of separation. The energy required to remove the outer electron from the Na atom (ionisation energy of sodium atom), leaving it a Na+ ion is about 5 eV; or Na + 5 eV ® Na+ + e
Bonding in Solids and Crystal Structures and Xray Diffraction
5
Similarly when the removed electron from sodium atom is added to chlorine atom, about 3.5 eV of energy (electron affinity of chlorine) is released. Cl + e ® Cl + 3.5 Thus a net energy of (5.0 3.5) = 1.5 eV is spent in creating a positive sodium ion and a negative chlorine ion at infinity. i.e., Na + Cl + 1.5 eV ® Na+ + Cl
Now the electrostatic attraction between these ions brings them to the equilibrium spacing ro = 0.24 nm and the energy released in the formation of NaCl molecule is called the bond energy of the molecule and it is obtained as follows: V= −
e2 (1.6 × 10 −19 ) 2 =− 4 π ∈0 r0 4π(8.85 × 10 −12 )(0.24 × 10 −9 ) 2.56 × 0.0096 × 10 −16 eV 1.6 × 10 −19
...(1.1.5)
= 2.56 ´ 0.0096 ´ 1016 J = − V = 6 eV
Thus the energy released in the formation of NaCl molecule from the neutral Na and Cl atoms is (5.0 3.5 6) = 4.5 eV. Schematically, Na+ + Cl ® Na + Cl + 4.5 eV ® NaCl ¬ 0.24 nm ® This means that to dissociate one NaCl molecule 4.5 eV energy is required.
1.1.6 CALCULATION OF MADELUNG CONSTANT AND LATTICE ENERGY OF IONIC CRYSTALS
The lattice energy of an ionic solid will differ from the bond energy of diatomic ionic molecules since, in the former case there will be interactions between more atoms. The cohesive energy of an ionic crystal is the energy that would be liberated by the formation of the crystal from individual neutral atoms. The arrangement of Na+ and Cl ions in a sodium chloride crystal is shown in Fig. 1.3. Each sodium ion in sodium chloride is subject to the attractive potential due to 6 chlorine ions each at a distance r. Thus the attractive potential at the sodium ion by the chlorine ion is U1 = − 6
e2 4π ∈0 r
The next nearest neighbours are 12 of the same kind of ions at a distance r 2 . Thus U2 =
12 e2 4π ∈0 r
( )
( 2 ) and so on.
75 which is close to the accurate value of 1.6 Applied Physics Fig.. This constant is called Madelung constant. 4π ∈0 r 4π ∈0 r ( 2 ) 4π ∈0 r ( 3 ) e2 12 8 6 + − + ... Thus the total potential energy is Ucoub = − 6e 2 12e 2 8e 2 + − + .3 Sodium chloride structure.. 1..747558 obtained for NaCl structure by the Ewold method. a = 6 − 2 3 2 All these relations are applicable only to univalent alkali halides (i.. 6 − 4π ∈0 r 2 3 2 = − Let 12 8 6 + − + . According to the scheme of Evjen. Thus Ucoub = − α as e2 4π ∈0 r The potential energy contribution of the shortrange repulsive forces can be expressed Urep = B rn .. a = 1.e. Z1 = Z2 = 1).
U is minimum and hence dU nB α e2 − n+1 = 0 dr = 2 4π ∈0 r0 r0 r =r0 i.(1.8) or Umin = − 1 1 − n Thus for one kmol of the crystal.. the coulomb energy is U0 = − α e2N A 1 1 − n 4 π ∈0 r0 .6) But at the equilibrium spacing r0.1. ..6) with r = r0. or nB α e2 = rn 4π ∈0 r0 0 n α e 2r0 −1 B= 4 π ∈0 n i.. ..9) There are two other contributions to the cohesive energy of an ionic crystal that have not been considered. Thus the total potential energy U of each ion due to its interaction with all other ions in the crystal therefore is U(r) = − B α e2 + n 4π ∈0 r r dU =0 dr .. one gets Umin = − = − α e 2r0n−1 α e2 + n 4 π ∈0 r0 4π ∈0 nr0 α e2 4π ∈0 r0 α e2 4 π ∈0 r0 + α e2 4π nr0 ∈0 ..1.1. which increases the cohesive energy and (b) the zeropoint oscillations of their equilibrium positions which decrease the cohesive energy.(1. (a) the van der Waals attraction between adjacent ions.e.(1..(1.1. Both of these effects being very small in ionic crystals and are usually neglected..e..1.7) Substituting this value of B in equation (1.Bonding in Solids and Crystal Structures and Xray Diffraction 7 where B is a constant and Urep is positive which increases rapidly with decreasing internuclear distance r..
bonds are formed in which covalency is not fully achieved and these bonds can break and reform fairly as in metallic . in this bonding. As we have seen carbon can exist in the covalent form and so it is an extremely poor conductor. This may happen between two atoms of the same type or different types. Having given up their valence electrons. In a covalent bond the electrons from the outermost shell are shared by both the atoms. In this case. because the electron gas permits atoms to slide fast one another by acting as a lubricant.7 THE COVALENT BOND The existence of compounds such as H2.8 METALLIC BOND AND PHYSICAL PROPERTIES OF METALS Metallic elements have low ionisation energies and hence. H2 + 4. The high electrical and thermal conductivities of metals follow from the ability of the free electrons to migrate through their crystal lattices while all of the electrons in ionic and covalent crystals are bound to particular atoms. N2 and O2 as well as bonds in atomic crystals such as diamond cannot be accounted for by ionic bonds because atoms of only one kind cannot produce ions of opposite kind by transfer of electrons. It is due to this reason that solids formed by such bond are usually called nonpolar substances. but are between the ions and the electrons. About 4. These electrons are loosely held by their atoms and therefore can be easily released to the common pool to form an electron cloud. it may also exist in an alternate form as graphite. Most of the atoms in metals have one or two valence electrons. it is now indicated . The bonds that exist between atoms of the same kind are called covalent bonds. However. H× H 1.5 eV energy is required to break one bond between the hydrogen atoms. Hence some energy must be spent to break the covalent bond in a hydrogen molecule into hydrogen atoms.5 eV ® H + H The covalent bond between the two hydrogen atoms in a hydrogen molecule is represented as: H:H as: It is desired to make clear that one electron has come from each atom. metals may be deformed without fracture.e. Therefore. the shared outer electrons belong to both the atoms and not to this one or the other.8 Applied Physics 1.074 nm. The balance between the attractive and repulsive forces in hydrogen molecule occurs at a separation of 0. i. It may also be noted in this bond. The electrostatic interaction between the positive ions and the electron gas holds the metal together. These are held together by forces that are similar to those of ionic bond in that they are primarily electrostatic. atoms of the same element or different elements give their valence electrons to form an electron cloud or say electron gas throughout the space occupied by the atoms.1.1. the atoms are in reality positive ions. Unlike other crystals.. both the atoms are neutral even after the formation of bond.
however. For this reason graphite is a conductor. just like the soldiers do on the parade ground.d is applied between any two points in a metal piece. The same free electrons are responsible for transferring thermal energy from places of high temperature to places of low temperature due to their mobility. copper and silver have these bonds. If a p. nickel. the electron gas flows from negatively charged part to the positively charged part.2. 1.Bonding in Solids and Crystal Structures and Xray Diffraction 9 Fig. The diffuse nature of electrons in the metallic materials make them opaque. Metals like sodium. In crystalline solids. This accounts for high thermal conductivity of metals. the solid state of matter can be put into two broad categories: the crystalline and the noncrystalline (or amorphous). bond. constituting electric current. they are distinguished from one another primarily by the degree of order exhibited by the arrangement of the fundamental particles atoms.4 Bonding in metals. The distinction between the two does not. molecules or ions comprising them. the atoms or ions (which may be compared with building blocks) are stacked in a regular manner.1 INTRODUCTION On the basis of structure.2 CRYSTAL STRUCTURES AND XRAY DIFFRACTION 1. depend on their external appearance or macroscopic form. When the regularity of the pattern extends throughout a . For the same reason the atomic planes can slide over each other without causing bonds to rupture thus making the materials ductile. instead. 1. have predominantly metallic bond with a significant fraction of covalent bonds. thus forming a three dimensional pattern which may be obtained by a threedimensional repetition of a building block or pattern unit. tungsten. The free electrons absorb light and do not permit it to pass through. The transition metals such as iron.
. 1. a crystal lattice. If r ′ is not identical with r for any arbitrary choice of n1. There are over 20000 crystalline substances in the crystal kingdom. The translation H H H H operation (vector) T is defined in terms of three translation vectors a. The size of grain in which the structure is periodic may vary from submicroscopic (many Angstroms) upwards and when it becomes comparable to the size of pattern unit. then it can be treated for many purposes a single crystal and would be so called. that is.g. ions. the H H H resulting point r ′(r ′ = r + T = r + n1 a + n2b + n3 c ) must be identical in all respects with the H H original point r. However when the atoms are not given an opportunity to arrange themselves properly. Such enumeration and classification provide a natural starting point for mathematical description of crystals.. In order to convert this lattice into a crystal structure. One then speaks of amorphous substances. the H H H vectors a . The translation H H H vectors a. b . Thus in this chapter we begin our study of the physical properties of crystalline solids by introducing the concept of crystal lattice and its application to the classification of solids. HT is applied to any point r in the material. In such materials the regularity or periodicity is interrupted at the grain boundaries though the structure may be more stable. n3. most of the solids of technical interest such as metals. By letting ns assume all integral values.1) where n1. ceramics. are not single crystals. These materials are called polycrystalline. the temperature of a liquid is dropped abruptly arresting the motion of atoms before they can rearrange themselves. we must locate atoms. the amorphous material may be formed. This repeating unit obeys the translation operation. but often consist of a large number of small crystal sections (grains) of various shapes and sizes packed to one another in a quite irregular way along the interfaces called the grain boundaries. However. we can reach an infinite. WhenHtheH operation. The repeating .10 Applied Physics certain piece of solid. b . or molecules on the lattice points.2. Modern theory of solids is founded on the science of crystallography. c are often called crystal axes and their directions are usually along the axes of the primitive unit cell the smallest repeating unit of the crystal containing lattice points H H only at its corners. This is because the energy of the ordered atomic arrangement is lower than that of an irregular packing of atoms. regular repeating array of units. n2. Nature favours crystalline state for solids. e.2 LANGUAGE OF CRYSTALS Crystals are identified by their geometrical appearance. ionic salts. which is concerned with the enumeration and classification of the actual structures of various crystalline substances. c are not translation vectors. The collection of all translation operations constitutes the translation group. one can no longer speak of crystals. n2. since the essential feature of a crystal is its periodicity of structure.(1. The geometry array of (lattice) points thus generated constitutes the lattice. n3 arbitrary integers.2.. group of atoms/ions. external surfaces are usually plane faces. b. c as follows: H H H H T = n1 a + n2b + n3 c . But how do atoms arrange themselves around each other in a crystal? A crystal may be considered as a regular array of unitssmallest groupings that repeat themselves in all directions in space.
then the array of points is a two dimensional lattice.5 Two dimensional array of points.Bonding in Solids and Crystal Structures and Xray Diffraction 11 unit assemblyatom. radical. 1. H We choose any arbitrary point O as origin and consider the position vector r1 and H H H r2 of any two lattice points by joining them to O. the space lattice may be defined as follows: Fig. molecules. 1. hence it represents a space lattice. For three dimensional lattice. It is obvious from the figure that the environment about any two points is the same. etc. atoms and molecules in the space.e. The crystal structure is thus given by two specifications: lattice + basis. H H H H T = n1 a + n2b + n3 c Hence it should be remembered that a crystal lattice refers to the geometry of a set of points in space whereas the structure of the crystal refers to the actual ordering of its constituent ions. ion. Lattice points are an array of points generated by the translation operation. The crystal is generated by applying to the basis the translation group of operations for the type of lattice under consideration. The Basis and Crystal Structure For lattice to represent a crystal structure. H H H T = n1 a + n2b H H where n1. n2 are integers and a and b are fundamental translation vectors characteristics of the array. a unit assembly of atoms or molecules identical in composition) called the . that is located at each lattice point is called the basis. Illustrations Let us now consider the case of two dimensional array of points as shown in Fig. we associate every lattice point with one or more atoms (i..5. If the distance T of the two vectors r1 and H r2 satisfies the following relation. In a mathematical form.
It is observed from the figure that the basis consists of three different atoms. while the lattice is imaginary. gives the actual crystal. etc. basis and crystal structure. Unit Cell and Crystal Lattice For discussing the unit cell. It can also be observed that basis is identical in composition. 1. In this way the fundamental unit ABCD is called a unit cell.6 Space lattice. 1. When the basis is repeated with correct periodicity in all directions.12 Applied Physics basis or pattern. Fig. In crystals like aluminium and sodium the basis is a single atom. 1. the whole crystal lattice may be obtained. Thus a unit cell is the smallest geometric figure. Thus lattice + basis = crystal structure Figure 1. The crystal structure is real. KCl. then by rotating the parallelogram by any integral multiple of vector H H a and b . If we consider a parallelogram such as ABCD with sides AB = a and AD = b. let us consider a two dimensional crystal in which the atoms are arranged as in Fig. the basis is diatomic whereas in crystals like CaF2 the basis is triatomic. Fig. in NaCl.7. the repetition of which gives the actual crystal structure.6 shows the basis or pattern representing each lattice point.7 Two dimensional arrangement of atoms . arrangement and orientation.
8(a) Three dimensional unit cell. c as concurrent H H H H H H edges and including angles a.Bonding in Solids and Crystal Structures and Xray Diffraction 13 The unit cell may also be defined as the fundamental elementary pattern of minimum number of atoms. 1. b. For a three dimensional case.8(b) Three dimensional unit cell. The entire lattice structure of a crystal is found to consist of identical blocks or unit cells. A three dimensional unit cell is shown in Fig. Fig. It should be noted that the choice of a unit cell is not unique but it can be constructed into a number of ways as A'B'C'D' or A"B"C"D" shown in Fig.7. 1. molecules or group of molecules which represent fully all the characteristics of the crystal. The unit cell should be chosen in such a way that is conveys the symmetry of crystal lattice and makes the mathematical calculations easier. a unit cell may be defined as that volume of a solid from which the entire crystal may be constructed by translation repetition in three dimensions.8(b). g between b and c . 1. 1. H H H The unit cell is a parallelepiped formed by the basis vectors a . the same procedure may be adopted. Fig. c and a and a and b respectively as shown in Fig. b . Thus in general. 1.8(a). .
Each space lattice can be described with reference to its unit cell. b and g.3. The points with identical surroundings are called lattice points.9(a). in which case the system is known as facecentred. however. The seven crystal systems and fourteen Bravais lattices are described in Table 1. 1. For example. some variations on this primitive system are also possible. Thus there are fourteen Bravais lattices.10. 1. The unit cell may be regarded as the fundamental building block of a crystal. Though not shown in the figure it may be remembered that an atom will be sitting at each corner of the cube in Fig. Fig. seven different systems of crystals are obtained by assigning different values to the edges a. b.9(b). If. three dimensional array of points in which every point has surroundings with that of every other point as discussed earlier. b. . the atomic arrangements must be described completely by specifying atom positions in some repeating unit of the space lattice. Mathematicians have shown a long time ago that there are only fourteen independent ways of arranging points in three dimensional space such that each arrangement conforms to the definition of a space lattice. c and angles a. The edges of unit cell must be vectors connecting any two lattice points.14 Applied Physics 1. 1. b and c such that the angle between b and c is a.3 CRYSTAL SYSTEMS AND BRAVAIS LATTICES The crystalline structure is often referred to as latticed structure. Since the regular pattern of atoms in a space lattice is regular. when several of such unit cells are placed with common surfaces of contact result into a crystal. only corners are occupied by atoms the system is known as primitive denoted by P. denoted by F. such a system is shown in Fig. For example the simplest of all these. The Bravais lattices describe the different arrangement in which lattice point can be arranged in unit cells. the centres of only two opposite faces are occupied additionally the system is known as base centred denoted by C. 1. that between c and a is b and that between a and b is g. When. Each unit cell can be represented by three intersecting edges a. This repeating unit of the space lattice is called a unit cell.1 and shown in Fig. 2. c and angles between a. cubic crystal system is obtained when a = b = c and a = b = g = 90o.1(b). This configuration is shown in Fig. Yet another variation of the crystal system is when an additional atom occupies the centre of the body of the unit cell denoted by I. additional atom may sit at the centre of all the faces.9 The axes and angles which describe a unit cell (b) A cubic unit cell.2. A space lattice is an infinite.
face centred Simple. base centred. 4. 5.1 Crystal systems and Bravais lattices Sl. body centred. body centred. Tetragonal Rhombohedral (Trigonal) Hexagonal Orthorhombic (Orthogonal) a=b¹c a=b=c a=b¹c a¹b¹c a = b = g = 90° a = b = g = 90° a = b = 90° and g = 120° a = b = g = 90o 2 1 1 4 6. 3. Monoclinic Triclinic a¹b¹c a¹b¹c a = b = 90o ¹ g a ¹ b ¹ g ¹ 90o 2 1 7 14 .Bonding in Solids and Crystal Structures and Xray Diffraction 15 Table 1. body centred Simple Simple Simple. No 1. 7. face centred Simple. base centred Simple Lattice symbol P I F P I P P P C I F P C P Number of lattices in the system 3 2. System Cube Axes a=b=c Angles a = b = g = 90° Bravais lattices Simple.
a = 2r.10 The fourteen Bravais lattices falling in the seven systems of crystals. It can also be observed that each corner atom is shared by 8 lattices. body centred cubic (bcc). The structure shown in the above figure teaches that eight atoms are arranged in a regular cube.2. i. Thus (1) volume of the unit cell is V = a3 . one atom at each corner. one corner of lattice atom shares effectively 1/8 atom to the unit cell under consideration. 1. 1.e. relatively few of these need concern us: about threequarters of the elements (mostly metals and a few semiconductors) used right from transmission lines to microinstruments in spaceship are metals or semiconductors. From the geometry of the cell it is clear that side of the cube is equal to twice the radius of the atom.e. The arrangement of atoms is repeated in all X.16 Applied Physics Fig. 1.4 STRUCTURE OF METALLIC CRYSTALS Many important properties of solids depend on their crystal structures. It is a cubic unit cell of parameter a.11 Simple cubic structure. Y and Z directions. Fortunately. 1. Simple cubic structure (Primitive) Fig.. The simple study of this simple structure is now discussed. i. hexagonal closepacked (hcp). a minor study of this structure theoretically will aid us to extend the frame work to calculate the packing fraction of other structures. These elements crystallize in one of the following structures: face centred cubic (fcc). or diamond cubic crystal structure (dc). Though only one well known element polonium crystallizes in the simple cubic structure..
Body centred cubic lattice (bcc) . Fig.52 or 52% 2.2. (CF)2 = (CA)2 + ( AF )2 (4r )2 = 2a 2 + a 2 = 3a 2 4r 16 r 2 = 3a 2 . n = PF = 0. PF = = = π V 3 ( 2r )3 a3 π 4π = = 0. Each corner atom in this structure is shared by eight cells an additional atom sits at the body centre well within the unit cell touching the eight corner atoms along the body diagonal and not along the edges as discussed in sc structure. 1.Bonding in Solids and Crystal Structures and Xray Diffraction 17 1 ×8 = 1 8 (3) nearest neighbours (or coordination number) = 6 (4) nearest neighbour distance 2r = a (5) the lattice parameter a = 2 r Thus the volume occupied by massive atoms in unit volume is called packing fraction.. Hence it is absolutely essential to have a geometrical sketch of the unit cell and an environmental study of the corner atoms and the atom sited at the body centre in order to calculate its packing fraction..(1. [Here ν is the volume of all the atoms in a unit cell and it is 1 × π r V 3 4 3 1 × πr v r3 4 3 i. a = 3 .2) Iron is the most common metal used to fabricate iron curtain and to manufacture different kinds of steel used in many nonbasic areas such as engineering and medicine crystallizes in bcc structure. 1..52 = 3×8 6 (2) number of atoms in a cell is. v 4 3 and that is equal to .e.12 Body centred cubic.12. The packing fraction of this structure is computed using the following data and by having a look of Fig.
(1) the lattice parameter. Here the lattice points (or atoms) are situated at all the eight corners as in the previous two cases. Compared with sc structure. Face centred cubic lattice (fcc) There are two forms of closest packing: face centred cubic (fcc) space lattice and hexagonal close packed structure.(1.F = = 3 3 = V 64r /3 3 64 × 3 × r 3 P . This lattice is also 8 known as a cubic F lattice. CN = 8 Now Density of packing or packing fraction. The face centre atom shares with two 1 unit cells.F = π 3 = 68% 8 .2. 3. 2r = . 2r = (2) the lattice parameter. V = a 3 = 4 3 πr 3 64r 3 3 3 (6) coordination number.3) Chromium and barium are the other examples. a = a( 3 ) 2 4r 3 1 (3) number of atoms in the unit cell. The atoms touch along the face diagonals. v = 2 × (5) volume of unit cell. Fig. The packing fraction is now calculated by the usual method.3 deals with fcc structure and helps us to find a way out to compute the packing fraction following the general definitions made in the previous cases. 2. a = 4r 2 a( 2 ) 2 (2) nearest neighbour distance. Hence the number of atoms in a unit cell is × 8 + 3 = 4.F = π 3 = 0. but also at the centres of the six faces. 2 = 1 + × 8 8 (4) volume of all the atoms in the unit cell.18 Applied Physics Thus (1) nearest neighbour distance.5..68 8 P . 8 3 πr v 8 × 3 3 πr 3 P . the packing fraction of this structure is 16% more.. Hence this bcc structure is called a closely packed structure while the other one is loosely packed structure.
(3) number of atoms in the unit cell = 4 3 (4) volume of all the atoms in the unit cell.4) copper. 2. CN = 12 Thus density of packing fraction.74 or 74% 6 4 3 P. Properties Diamond cube (dc) Simple cube (sc) Body centred cube (bcc) a3 2 Face centred cube (fcc) a3 4 Hexagonal close packed structure (hep) 1..2.. Table 1. = 4 × π r = v (5) volume of unit cell. aluminium and lead are some examples of this structure.(1.) .F = v 16 πr 3 2 2 = = V 3 ( 4r )3 2π = 0..2: Comparison of cell properties of some crystal lattices S. No. V = a 3 (6) coordination number. Volume of unit a3 8 a3 1 cell Number of atoms per cell 3 3 (a 2 c ) 2 6 (Contd. P .13 Face centred cubic structure..Bonding in Solids and Crystal Structures and Xray Diffraction 19 Fig.F = . 1.
34 16 a a 3 2 a 3 4 π 3 = 0. Iron.5 MILLER INDICES Various properties of crystals. Aluminium. Number of atoms per unit volume 4. a 3 4 a 3 8 π 3 = 0. Germanium Polonium Sodium.14 The (3 6 2) plane.74 6 Magnesium.52 8. In a crystal there exists directions and planes which contain a large concentration of atoms. Fig.2.68 8 a 2 2 a 2 4 π 2 = 6 0. a 2 a 2 π 2 = 0. 1. Silicon and Chromium Copper and Diamond Lead 1. Zinc and Cadmium 7. .20 3.74 a 6. mainly mechanical properties are connected with the structure of the crystal through the help of crystal directions and planes. Miller evolved a method to designate a set of parallel planes in a crystal by three numbers (h k l) known as Miller indices. Number of nearest neighbours Nearest neighbour distance (2r) Atomic radius Applied Physics 8 a3 4 1 a3 6 2 a3 8 4 a3 12 4 3 (a 2 c ) 12 5. Xrays are easily diffracted through planes containing large concentration of atoms. Atomic packing factor Examples π 3 = 6 0.
The direction [1 0 0] is the line passing through origin and point Q. 1 b units on the baxis and 4 c on the caxis. Y. The direction [1 1 1] is the line passing through the origin and point P. The plane makes intercepts on all the axesat 1 1 3a units on the aaxis. 2 . then its intercept is at infinity and its reciprocal is therefore zero.1. 1 . ( ) Crystal directions The crystal directions are usually given in a square bracket like [ ]. c): . or 1 .15 Crystal directions. Y. Multiplying these three terms by 9. and Z axes. Direction [101] is the line passing through origin and R. The point R is at distance of 101 form X. 2 . we get repeat units a. 1. The point Q is at a distance 100 from X. The point P is at a unit cell distance from each axis.15. 1 4 3 3 3 9 2 2 the integers (3 6 2). 1. and Z axis. which are called Miller indices of the plane. thus 1 2 3 . the (0 0 1) plane is parallel to aand baxis and intercepts the caxis.Bonding in Solids and Crystal Structures and Xray Diffraction 21 Consider the plane shown in Fig. Negative intercepts are written with a bar over them. In Fig. In short Miller indices are defined as the reciprocals of the intercepts made by the plane. so a zero in the Miller indices of a plane means that it must be parallel to that axis. It is easier to specify crystal direction on a unit cell. For example. If a plane is parallel to a given axis. three different directions are shown in the orthorhombic lattice. b.2. The Miller indices 2 2 of the plane are found by taking the reciprocals of the axial intercepts (ignoring the lattice 1 1 1 1 . Fig.7. . on the crystallographic axes when reduced to smallest numbers.
16. (iv) If (h k l) are the Miller indices of a plane. crystal axes are taken as base directions [3 3 3] or [2 2 2] direction are identical to [1 1 1] direction. [1 1 1] is used to specify direction. (8 4 4) or (4 2 2) or (2 1 1). k and l equal segments. Thus the Miller indices define a set of parallel planes. This important equation may be obtained as follows: (h k l) represents the Miller indices of the plane ABC. Interplanar spacings In a cubic system. i. k and l are the indices of the plane and a is the lattice constant. then the plane cuts the axes into h. (iii) If the Miller indices of two planes have the same ratio. (v) In specifying crystal direction. See Fig. 1. . 1. then the planes are parallel to each other. (ii) A plane parallel to one of the coordinate axes has intercept of infinity. This plane belongs to a family of planes whose Miller indices are (h k l ) because Miller indices represent a set of planes.e.. the distance between two successive planes can be calculated by using the relation dhkl = a h + k2 + l 2 2 where h.. In such cases lowest combination of integers i.16 Interplannar spacing in cubic crystal.e.22 Conclusions Applied Physics (i) All the parallel equidistant planes have the same Miller indices. Fig.
(1. cos β′ = 1 and cos γ′ = 1 OA OB OC .Bonding in Solids and Crystal Structures and Xray Diffraction 23 Let α′. and ON Thus OA = a a a . The intercepts of the plane on these crystallographic axes are: OA ′ = 2a 2b 2c . and g ) be the angles between coordinates axes XYZ respectively on ON'... b. OB' = OR and OC' = OP) . OB ′ = and OC ′ = h h l (with OA' = OQ.5) Also Again and Thus cos α′ = (ON)2 = x2 + y2 + z2 with ON = d1 cos α′ = x y z .2. OB = and OC = h k l d1 d d . 2 d1 2 2 2 2 2 2 a2 (h 2 + k 2 + l 2 ) = 1 2 d1 = a2 (h 2 + k 2 + l 2 ) a (h + k 2 + l 2 ) 2 d1 = Let ON' = d2 be the perpendicular of the next plane PQR parallel to ABC.1). cos β′ = cos γ ′ = d1 d1 and d1 2 2 d1 = d1 (cos2 α′ + cos2 β′ + cos2 γ′) d1 = d1 [cos2 α′ + cos2 β′ + cos2 γ′]1 / 2 In the Cartesian system of coordinates the sum of the squares of the direction cosines is equal to 1. (2. Substituting this in eqn. β′ and γ′ (different from interfacial angles a. we get d1 d1 d1 OA + OB + OC = 1 d1l d1h d1 k a + b + c =1 For cubic system.7.
. 1. Certain combinations q.6) 2 2 2 2 2 2 (ON ′)2 = d2 cos α′ + d2 cos β′ + d2 cos γ′ with ON' = d2 But cos2 α′ + cos2 β′ + cos2 γ′ = 1 Substituting this in Eqn. with the resulting increase in intensity of diffracted Xrays. These different sets of planes make different angles q with the direction of Xrays.2. Each set of plane will pick up various values of wavelengths. Braggs condition is satisfied. the interplaner spacing can be calculated from Braggs equation. which can satisfy Braggs law..(1. This method is called Laue technique. for cubic system 2 d2 (h 2 + k 2 + l 2 ) = 1 ( 2a )2 2 2 2 d2 = 2a (h + k 2 + l 2 ) 2 Thus the interplanar distance between two adjacent planes of Miller indices (h k l) in a cubic lattice is given by d = ( d2 − d1 ) = a h + k2 + l 2 2 .2.2.6 XRAY DIFFRACTION A fine beam of Xrays fall on the single crystal. Thus each set of plane will produce a spot which fulfils Braggs law.. the rays meet Braggs planes having different interplaner spacings d.. The crystal is rotated in such way that. By measuring the value of angle q. While passing through the crystal.(1.6 and simplifying one gets d2 h d2 k d2l 2a + 2b + 2c = 1. at some position of the crystal. A number of polychromatic Xrays strike at 90º on the plane of a crystal under study. Laue method is one of the principal methods used for the analysis of crystal structure.2. cos β′ = 2 and cos γ′ = 2 ′ ′ OA OB OC ′ .24 Applied Physics and cos α ′ = d2 d d .7) 1. (a) Laue method to study crystal structure A single crystal is placed in the path of Xrays beam and the glancing angle q is kept constant.. and d satisfy the conditions of Braggs law.
There will be reflection. passes through the specimen and the unused part of beam leaves through hole b. As different wave lengths are included in the primary Xray. 1. which are less pronounced. In the powder technic. thus. Thus tan 2θ = AB . around this central spot as shown in Fig. The Xray beam enters through hole a. Consequently the reflected rays will not be in the form of parallel . 1. As there are a large number of randomly oriented crystals in the powder. Let A be the spot obtained on the photographic plate. The specimen (spindle. if Bragg condition is satisfied. a sample of material is ground into fine powder. there are many possible orientations of this set of planes for same angle q.17 Xray diffraction (Laue method). they will produce spots. Let the incident rays make an angle q with a set of parallel crystal planes. The powder is then placed in a capillary tube or pasted on thin wire or pressed and cemented into a thin spindle. One of the planes considered as the plane for diffraction makes q with the incident ray. they produce a black spot at point B on the photographic plate PP.Bonding in Solids and Crystal Structures and Xray Diffraction 25 Fig. we can find the value of angle q for corresponding plane. 1. AB = R tan 2θ R By measuring AB and R. This powder specimen is placed at the centre around which a strip of circular photographic film is positioned as shown in Fig. This method is usually used for single large size crystal. The crystalline material is available either in the form of very small crystals or in powder form. etc) is slowly revolved inside the specially constructed circular camera called the powder camera.18(a). When primary rays pass though the crystal. A narrow beam of monochromatic Xrays is allowed to strike the specimen (in capillary tube or wire or spindle) through a small hole.17. (b) Powder crystal method (DebyeSherrer method) This technique is used when single crystals of large size are not available.
The greater the value of q. the value of S is related 2 sin θ S µ 4q 2π R ∝ 360 o S 4θ θ = = o o 2π R 360 90 . that would satisfy Bragg condition. The apex of the cone is the point of contact of xrays with the specimen.e. This circle will interest the film strip at midpoints between the incident hole a and exist hole b. The angle between the surface of cone i. the farther will the arcs from the exist hole. For each combination. back reflection takes place. reflected ray and exist of beam is 2q or we can say that apex angle is 4q. When the Bragg angle is greater than 45o. For a fixed value of n (say n = 1). there are so many combinations of d and q. Fig. the cone will take the form of circle. the smaller will be the interplaner spacings according to d = with q as below: λ . 1. In case the Bragg angle is 45o.18 Xray diffraction (Powder technique) (b) photographic film (record). one cone of reflection will be there and hence so many cones of reflection are emitted by the specimen. The other pairs of arcs beyond this pair are due to larger value of q.18(b).26 Applied Physics beam but they (reflected rays) will lie on the surface of a cone (like generators of a cone). If the distance between a pair of arc is S. As the film is of narrow width only a part of each reflected cone is recorded on the film which is positioned around the camera. The first pair of arc on each side of exit hole is due to smaller value of q. The recorded lines are in the form of pair of arcs as shown in Fig. the reflected cones are formed toward incidence hole a.. 1.
This Xray diffraction technique is suitable for (i) identification of elements and compounds. along with other known data (n and l) is substituted in Bragg equation and the interplaner spacing can be calculated. The half of this distance gives the magnitude of angle q in degree. the changes in the lattices can be studied. 1.19 Experimental arrangement (Powder crystal method). Xrays from the tube are allowed to pass through filter F which absorbs all except one wavelength of incident Xray beam of monochromatic one. The value of q. 1. S= 2π R θ Fig. .19. (a) By taking the photograph before and after heat treatment or cold working of a crystal. This monochromatic beam is now passed through two fine slits S1 and S2 cut in lead plates and then fall on powder crystals C. By measuring the intensities of arcs with the help of diffraction meter. because the powder patterns are unique for each substance.Bonding in Solids and Crystal Structures and Xray Diffraction 27 90 o The standard diameter of camera is 57. (b) The dimensions of a unit cell and type of lattice can be determined for simple cases. (c) We can distinguish between crystalline and amorphous substances. A photo film is arranged around the inner surface of the camera as shown in the figure.3 mm. the following information can be obtained. as crystalline substances produce lines (arcs) on photo film while amorphous substances do not. then 2p R is equal to 57.14 = 180o S = 2q degree The distance S is measured in mm. (ii) determination of orientation of a single crystal (iii) determination of structures of crystals of high symmetry (iv) estimation of grain size of polycrystalline materials.3 × 3. The experimental arrangement of powder crystal method is shown in Fig.
1 1.1.22 has been taken from the B.1.2.1. May 1990) 1.1..17 Explain electron affinity in bonding.18* What is meant by coordination number in solids? 1.28 Applied Physics SHORT QUESTIONS 1. London).1. (Anna. Give an example. U.K. (Anna.3 1. BE. BE.1. November 1995) (Anna.7 1.1.2 1. November 1993) Why high external energy is required to melt ionic crystals? Reaction between ionic compounds in solution state is high. Explain the features of metallic bond with illustrations..22* Give reasons: (i) magnesium oxide is bonded ionically (ii) van der Waals bond is weak (iii) liquid carbon tetrachloride cannot conduct electricity (Question 1. BE.1. Explain why they do not collapse? 1.1.1. (Anna.1. April 1983) . November 1992). Tech.1. compute the energy required in eV to break one H H bond.1. 1. 1.1. question paper of Imperial College of Science & Technology.8 Explain electric dipole.. Discuss the interaction between the atoms in a diatomic molecule with suitable graphs. 1.10 Explain covalent bonds with two examples. U.13 List out the different characteristics of hydrogen bonded crystals. 1.12 Explain van der Waals forces and molecular crystals. U. U.1. BE. U.16* Discuss the characteristics of hydrogen bonded crystals.15 The materials having metallic bonds are always opaque. 1.9* If 440 × 103 kJ of energy is required to break the H H bonds in a kmol. U. U..1.4 Differentiate primary bonds and secondary bonds. 1.2 Define crystal structure. crystal lattice and Bravais space lattice.1.. April 1988) 1. (Anna. Find the radius of the interstitial sphere that just fit into the void at the centre between the body centred atoms of the bcc structure.14 Experiments suggest that CCl4 has no net dipole moment. BE.5* Show that the Madelung constant for a linear ionic solid having 2N ions of alternate charge ± e is 2 ln 2. 1.1. BE April 1999) In crystals there is an attractive interaction of one kind or other which is quite appreciable for nearest neighbours.19 What are the characteristic features of covalent bonded crystals? (Anna. April 1990) 1. Give reasons.1. U.1 1. BE.. BE. U... November 1989) 1. (M.2.1.11 Describe the formation of hydrogen bonded crystals.20 Describe briefly metallic and van der Waals bonds. November 1986) 1.1.. (Anna.6 1. BE and Parttime BE. 1.21 Compare and contrast the characteristics of ionic and covalent bonds. BE. 1. Give one line answer. Give the reasons. (Anna. (Madras U.1.1. 1..
Tech.2..2.9* Show that for a cubic lattice. 1.856. NA is Avogadors number and r is the density of the material (Anna. Tech.5 nm. BE.18* Give the general explanation of closest packing with suitable figures. U. (REC.2.5* Distinguish space lattice and crystal structure. Explain. (M. 1. lattice and crystal structure.2.2. Jaipur. B.2..3 1. .Tech. 1/3 1.. 1.19 What are Miller indices? Explain Burgers vectors./B. BE. (b) germanium.2. 1..63.20 Silicon crystallizes in dc structure. April 2004) 1. U. 1.2.16 Explain coordination number..15 Explain rotationinversion axis in a cubical crystal. May 2002) 1.14 If the height of the unit cell of zinc (hcp) is 0.2. November 1996) Describe the seven crystal systems. U.2. (c) barium. May 1996). Tech. What are Schottky defects. U. How many unit cells will be there in a cubical crystal of side 0.11 Distinguish primitive cell and unit cell. (d) zinc.Bonding in Solids and Crystal Structures and Xray Diffraction 29 1.2.2.. (JNTU.22 The theoretical value of c/a ratio for zinc is 1. Tech/BE May 1984) 1.12 List out the different kinds of symmetry elements and their total number in a cube. But the actual value of c/a for zinc in hcp structure is 1. Explain the terms basis. BE/B. U.7 1. 2002) 1.25 Give the crystal structure of the following: (a) gold. Explain symmetry elements and symmetry operations in crystals.2.2.2. 1. U... the lattice constant a is given by nM A a= N Aρ where n is the number of atoms in a unit cell. B.23 Define atomic packing factor. BE.8 Distinguish crystalline and amorphous substances.2. (Anna. (Anna..2.2.2.24* What are Miller indices? How are they obtained? (JNTU. BE/B.17 What is meant by atomic radii in a crystal? How many atoms are there in the unit cell of diamond? 1.2. December 2001) Get the relation for the radius of the atom in terms of lattice parameter in fcc structure. 1. U. compute the radius of zinc atom.2.21 What is Bravais lattice? Draw the planes (1 1 0) and (1 1 1) in a cubical unit cell. nearest neighbour distance and packing factor with the help of a highly crystalline solid.13 Show that 3 a ratio for an ideal hexagonal crystal is c 8 (M. 1979) 1.10 How many atoms are there in the unit cell of diamond? 1.2. 1. (Anna.495 nm. U.4 1. BE/B.. (Anna.2. If the lattice constant at 25 oC is 0. November 1998) 1.6 1. BE April 2001). Tech/BE. May 1997) 1. (Anna.5 cm. MA is the atomic weight.
2.32 If 0. B. iii) unit cell. U.. 1998) Na+ ions. 2002) 1. ii) space lattice. compute the shortest distance between (IIT Mumbai. May 2001) 1.. 4 π ∈0 r0 2 3 4 ..5* Let us take Na+ at the point 0.. Tech/BE. (Anna. (Anna. (University of Groningen. May 1990) 1.27 Explain the terms i) basis. BE/B. Tech.34 Show that the Miller indices are the same for a family of crystallographic planes which are parallel to each other.K. 1989) 1.2. b and c in fcc structure. BE. find the distance between the parallel planes (1 1 1) and (2 2 2). (JNTU.30 Name different kinds of symmetry elements that are present in cubic crystal giving the total number..56 nm is the edge of the unit cell of NaCl. U. Tech. Also get the density of atoms in this plane. Netherlands. BE. If the radius of the atom is r. November 2003) 1. The interaction between this and the nearest chlorine ions at r0 is − e2 e2 2e 2 + − =− 4π ∈0 r0 4π ∈0 r0 4π ∈0 r0 Similarly the repulsive energy due to the two positive ions at a distance 2r0 is and that due to the next set of Na+ ions is − all the ions in the linear array is − 2e 2 4π ∈0 2r0 2e 2 .33* Obtain the Miller indices of a plane which intercepts at a.2.G. U.26 What are Schottky defects? How are they formed? Applied Physics (Anna.31 Discuss dc structure and get its packing factor..30 1.2.2.2.2. (M. B.28 Copper crystallizes in fcc structure.. University.2. Thus the total energy due to 4π ∈0 3r0 1 1 1 e2 2 1 − + − + .29 Draw planes (1 1 0) and (1 1 1) in a cubic crystal.2. 2002) 1. May 1989) Answers to the starred questions 1. U. 1. (Bangalore University. 1.1.
This must be equal to the number of atoms in the unit MA A A = n.5* Space lattice is nothing but the geometry of a set of points in space whereas the crystal structure denotes the real ordering or arrangement of the constitutent atoms or ions.38 1. M ρN A A ρN a3 M n M An a= ρN A 1/3 Answer . (ii) they have increased binding energy in comparison with similar molecules without hydrogen bonded ones. 1.. a3 = i. N A is Avogadros number. r and a be the atomic weight.1.2.e. Hence the energy required to break one H H bond is 6. (iii) they have weak binding..22* (i) because magnesium and oxygen are both divalent 2Mg + O2 ® Mg++ + 2O ® 2MgO (ii) because it bonds only molecules together (iii) because it does not contains C 4+ and Cl ions 1. Thus MA (molar volume) contains NA atom ρ a3 will have cell say n ρN A a 3 atoms.2. (iv) they have low electric conductivity and poor thermal conductivity.6 × 10 −19 440 × 106 = 4.6 eV 1. e2 (2 loge 2) 4π ∈0 r0 a = 2 ln 2 = 1. density of the element and a is the lattice parameter of the unit cell and n be the number of atoms in the unit cell.1.6 eV Ed = 4. (v) they are transparent.16* (i) they have the tendency to form groups of many molecules.02 × 1026 × 1.e.18* It is the number of atoms around an atom or the number of atoms which are just in the neighbourhood of atoms.9* Let MA.9* The energy required to break 6.1.Bonding in Solids and Crystal Structures and Xray Diffraction 31 = − i. 1. 1.02 × 1026 bonds is 440 × 106 joule.1.
24. z). 1. or lattice parameters along the axes. y and z axes. i. x y z 2a 3b c pq qb rc (b) Express the intercepts as multiples of the unit cell dimensions.18 Closest packing of spheres in twodimension and in threedimension. Fig.. 2.* Let a plane cut the axes at 2a. 2a a 2 3b b 3 c c 1 .e.32 Applied Physics 1. (a) Determine the coordinates of the intercepts made by the plane along the three crystallographic axes (x. 3b and c on x.2. Under this each object will be in contact with maximum number of like objects. y.18* Closest packing is a way of arranging equidimensional objects such that the available space is more efficiently filled.2.
Thus Miller indices may be defined as the reciprocals of the intercepts made by the plane on the crystallographic axes when reduced to smallest numbers.Bonding in Solids and Crystal Structures and Xray Diffraction 33 (c) Determine the reciprocals of these numbers 1 2 1 3 1 (d) Reduce these reciprocals to the smallest set of integral numbers and enclose them in brackets.2.33* a a a a a 1 (1 This plane is shown below. 1. a a 1 1 a a 1 1) The face diagonal is Base calculation : 2×a AO a 2 cos 60° = AO = α 2 cos 60° 2 × AO = a 2 × 2 × 1 = 2 2a . 6× 1 2 6× 1 3 6×1 (3 2 6) In general it is denoted by (h k l).
.34 The number of atoms in the plane is.2 1. Applied Physics n = × 3 + 1 = 2 atoms Height of the triangle. BE. (Anna.1. 3 H 1 6 1 2 cos 30° = 2 = a 2 or H 3 = a 2 1/2 Area = 1 1 3 × 2 × AO × H = 2a 2 2 2 2 4r 3 2 a with a = 2 2 1/2 = Thus 3 16 r 2 Area = 2 2 = 4r 2 3 The planar density of (1 1 1) plane is 2 4r 2 3 = 0. . M.. U.3 Describe the formation of NaCl lattice from neutral sodium chlorine atoms with suitable figures and equations. (Anna.Sc.288 r2 Answer REVIEW QUESTIONS 1.1. U. November 1984) What is meant by bond energy of NaCl molecule? Give the important steps to calculate the lattice energy of ionic crystals and hence obtain the final expression for the cohesive energy per kmol of the crystal.1 The potential energy of a diatomic molecule is given in terms of the interatomic distance r by the equation U(r) = − a b + n m r r Obtain the relation for the equilibrium spacing of the atoms and hence get the expression for dissociation energy.d = 0.1.288 r2 p. November 1983) 1..
2. (JNTU. November. (Calicut.1 1. Give two examples in each structure. B. May 2001) 1.2.. May 2001.U. (M. May 2002) . basis. Tech. BE.9 1.7 Define Miller indices of a lattice plane and write the equation to a family of planes represented by the indices (h k l). Explain with neat sketches the different imperfections in a crystal. IIT Delhi. May 1992). Show that an actual crystal cannot possess a fivefold rotational symmetry..2..2.2. 1994) 1. Compute the distance between the base and middle plane containing the three atoms. April. Tech.6 C 1. Anna U. l between adjacent (h k l) planes is given in terms of the cubic edge a. BE.2. (1 1 0) and (1 1 1) planes in it.2. BE.2. by dhkl = a h + k2 + l2 2 (M. (M.U. April 1994) 1.5 1. k.4 1. 2b on the baxis and 3c on the caxis. What is meant by symmetry elements and symmetry operations? Discuss the various types of symmetry elements in a cubic crystal. The radius of the atom is 0. BE.G. Calculate the ratio of the number of vacancies in equilibrium at 300 K in aluminium to that produced by rapid quenching from 800 K. (Metallurgy division. UK. Zinc has hcp structure. Compute the packing factor of bcc structure.1.12 Explain the dimensions of a unit cell. Find the Miller indices of a crystal plane that makes from some origin an intercept of a on the aaxis..2.. BE. (M. Name the seven crystal systems and give the relation of lengths of axes and the relation of angles between the axes of a unit cell in each type.2. Discuss the seven systems of crystals and the fourteen types of Bravais lattices with suitable figures.4 1..U. BE. November 1990) Discuss the various symmetry elements associated with a crystal.153 nm. May 1986) 1. Show that for cubic crystal the distance dh.. 1999. What do you understand by Madelung constant? How madelung constant can be computed? Explain the terms: lattice. M. Tech. 1992) 1.11 What are Miller indices? Draw neat diagrams to indicate Miller indices of some important plane systems in a simple cubic crystal.U. Derive an expression for the edge element of a cubic crystal in terms of the properties of the crystal material.K. U.10 Define space lattice. April. Draw the figures of a simple cubic crystal and indicate (1 0 0). Obtain the coordination number for bcc and fcc lattices.. (M.2.3 Explain the difference between ionic and covalent types of binding. University of Manchester./B. April 1982.663 and the density of a atomic packing equal to that of the facecentred cubic structure.2. P.U. why this structure is a closely packed one and not a closest one? Show that an ideal hexagonal close packed structure is 1.2 1. BE. Enthalpy of formation of vacancies in aluminium is 63 kJ/mol. May 1992) Estimate the fraction of total volume occupied by atoms in body centred and face centred cubic structures.U. B.8 Explain how Miller indices of a set of planes in a crystal are determined. BE. (JNTU. structure and unit cell.Bonding in Solids and Crystal Structures and Xray Diffraction 35 1. BE.
2.20 Explain primitive cell and unit cell. Copper has fcc structure and atomic weight of copper is 63.13 What are point. Derive an expression for the number of Schottky defects in equilibrium at a temperature T. What are Miller indices? In a simple cubic lattice with lattice parameter a.2.16 What is Bravais lattice? What are the different space lattices in the cubic system? How many lattice points per unit cell are there in each of these lattices? Deduce an expression for planes of the (h k l) type in the case of a cubic structure. B.2. BE. (2) unit cell.. What is the wavelength? (M.19 Show that the atomic packing factor of fcc and hcp structures are the same. May 1990) 1. line and surface imperfections formed in solid materials? Illustrate these imperfections with suitable sketches.. (Anna U.B: The first part of this question is not worded nicely) 1. (JNTU.2o for the d111 spacing of the chlorine ions. May 2003) 1. 1.U. (1 0 2).24 Draw the following planes in a cubical unit cell (0 1 1). BE.. 1.71 Ao was directed at . December 2003. (Anna U. Bring out the differences between edge dislocation and screw dislocation. April 1985) 1. 2002) 1. BE. 2004 N. BE. the lattice constants are given by a = and a = 4r 2 4r 3 respectively where r is the atomic radius..74. 2000) 1. Explain the following terms used in crystallography: (1) primitive cell. BE. N.2. The fraction of vacancy sites in a metal is 1 × 1010 at 500oC..2.54.B: Some data are missing in the second part of the question).2.23 Calculate APF value for fcc structure. November 1992) 1. Classify the important types of crystal imperfections. N. a radiation of wavelength... B.14 Show that for bcc and fcc crystal structure. 1.2..2. The diffraction angle is 5.22 What are Miller indices? How are they obtained? Explain Schottky and Frenkel defects with the help of suitable figures. Prove that five fold rotation axis is not compatible with a lattice.2. May 1989.. Sketch a unit cell of fcc lattice. (3) coordination number and (4) relative density of packing. What will be the fraction of vacancy sites at 1000oC? (JNTU.U. In an xray diffraction study.2. (1 3 2) and (1 1 2). (Anna U.2. BE. VTU. December 2003. Tech.17 Discuss in brief the type of bonding in a molecule of water.63 Ao is used to measure the wavelength of xrays. How they are determined? (Anna U.. BE.15 Explain how xrays are used for determining the crystal structure.2.36 Applied Physics 1.18 What is packing factor? Prove that the packing fraction of hcp is 0. (Anna U. what is the interplaner distance between (1 1 1) type planes. BE.B: The sentence in the last part must be how they are obtained?). (Anna. April 1994) 1. (Anna U.21 Explain the significance of Miller indices. A sodium chloride crystal of lattice constant 5. Tech. What are Miller indices? Explain. 1.
β . The potential energy due to repulsion between electrons is given by U r = (Lincoln Laboratory.02 × 10 −9 r2 = = 0. −9 = (1. BE.02 × 109 newton when the two ions just touch each other.U.26 Discuss Braggs law of xray diffraction.e. Describe the powder method to determine crystal structure.1.276 nm r =r(Na+) + r(Cl) r(Cl) = 0. The equilibrium distance between ions is 0. 1989). US. Massachusetts Institute of Technology..e. −9 F = 3.85 × 10 12 × r 2 2..2 Compute the net potential energy of a simple Na + Cl ion pair. July 2004) 1.181 nm Answer i. It was found that the first two Bragg reflections occur at angles of 30o. If the ionic radius of Na is 0.. (VTU.28 nm. what is the radius of Cl? (M. BE.14 × 8. TechMid semester.02 × 10 i.74. B. 1.276 0.095 r(Cl) = 0.Bonding in Solids and Crystal Structures and Xray Diffraction 37 a cubic crystalline sample. November 1995) PROBLEMS AND SOLUTIONS 1.25 Discuss the crystal structure of diamond.2. July 2004) 1. (VTU.. r8 .1 The force of attraction between ions of Na and Cl is 3.56 × 10 −38 4 × 3.85 × 10 −12 × 3. Determine whether the crystal is bcc or fcc structure.095 nm.2. Discuss Braggs spectrometer and explain how it is used to verify the Braggs law. Show that the packing fraction of fcc is 0.1. 35o 17¢ respectively. (Anna U. Five year BE 1980.02 × 10 = Solution: 4 π ∈0 r 2 Z1Z 2e2 In this case Z1 = Z2 = 1 Hence 3.0076 × 1017 or Thus Hence r = 0. AMIE. Winter 1999). BE.6 × 10 −19 )2 − 4π × 8.
02 × 10 −9 8 8b r9 But r = r0 = 0.02 × 10 −9 8 0. Z1 = 1. then Ua = − Z1Z 2e2 0 Applied Physics ∫ F1dr = ∫ 4π ∈ r2 dr In the case of Na+ and Cl ions.28 × 109 metre b= (0 .289 × 10 −81 × 3.02 × 109 = − b= r 9 × 3.28)8 × 10 −72 = − 2. Ua = 0 and hence C = 0 Ua = Ua = U = Ua + Ur = Fr = d b 8b 8= − 9 dr r r But Fa = Fr at the equilibrium position with Fa = 3.38 Solution: If F1 is the force of attraction between the ions.6 × 10 U= 4π ∈0 r0 ( −19 2 ) + b r08 + 4 × 10 −96 (0.02 × 109 N (taken from the previous problem). Z2 = 1.85 × 10 −12 × (0.02 = 8 8 = b = 4 × 1096 Thus 1 × ( −1) × 1.56 × 10 −38 4π × 8.02 × 10 −9 0. Thus Fr = 3.28 9 × 10 −90 × 3 .28 × 10 −9 ) .28 × 10 −9 )9 × 3. Hence Ua = Z1Z 2e2 +C 4π ∈0 r Z1Z 2e2 4π ∈0 r Z1Z 2e2 4π ∈0 r Z1Z2e 2 b + 4π ∈0 r r 8 When r = ¥.
one gets r = 0..235 nm dU (0 .52 = eV with r in nm 4 π ∈0 r r (r + r − r ) 2.0875) nm = 0.. (2).52 r + A0 exp (0.52 + A0 exp a c r ρ Now 6. B. C= 1.61) − i.047 ) A0 exp ρ = 31.(3) Substituting this in Eqn.025 nm Substituting r in Eqn. E.69 r . then determine Ao and r for NaCl if the cohesive energy per ion pair is 6.282 nm..3 × 10 −19 joule −19 U = − 7.61 eV and 0.282 nm = 0 = 0 + 2 − ρ exp ρ r =r0 r0 or (0.52 A0 dr with r0 = 0. (3). as 6. C and R are ionisation energy of Na.(2) ra + rc = (0..3 × 10 J Answer 1.235 − r0 ) 2.61 eV and the interatomic separation is 0.14 − 3.61 = (5 .1475 + 0. The ionisation energy and the basic radii of Na are 5.75 e 2.e.Bonding in Solids and Crystal Structures and Xray Diffraction 39 = − 8.53 2.14 eV and 0..235 − r ) ρ .61 = 1. IITMumbai. coulomb energy and repulsive respectively.1475 nm respectively.3 × 10 −19 + 1 × 10 −19 = − 7.146 eV Answer Answer .1.. we get A0 = 5..875 Å respectively where as the electron affinity and the basic radii of Cl are 3. (UPSC May 2000. Tech. electron affinity of Cl.(1) where I. May 1992) Solution: Cohesive energy per ion pair is U =IEC+R ..3 (ra + rc − r ) where ra and rc If the repulsive energy is of the MottGurney form A0 exp ρ are the basic radii of anions and cations respectively.
4 Applied Physics Calculate the ratio of ionic radii for an atomic coordination number of three as shown in figure. Karnataka.1.1.T. (V.02 × 1023 = 1. 1 500 × 6. Rudden used to add 500 cc of water to 500 cc of milk every time to prepare tea in his shop.U. R R r = 0. Can you suggest a method to estimate the number of water molecules added each time? Yes sir. I can suggest a small formula to calculate the number of molecules present in 500 cc of water.154 R Answer 1.67 ´ 1025 water molecules.5 Mr.40 1.866 R +r 1 = 1.02 ´ 1023 water molecules. If M and r are the molecular weight and density of water.. Thus M is the molar ρ Solution: 18 cc of water contains 6. BE May 2002) Solution: cos 30° = R +r R R = 0.154 − 1 = 1.67 × 1025 Answer .866 = 1+ r r = 1. then volume of water.154.154 0. 18 Hence 500 cc of water will have 1.
B: An apple in a day keeps the Doctor away. . Differentiating this. Similarly pumping 5 × 10 25 (1. six cations and an anion. The Open University.5 litre) molecules of water into the stomach every day makes all the vital organs below the diaphragm to function with pleasure and with least resistance. (Department of Chemistry.1. Tech.1.6 The total energy per kmol of a crystal is given by the equation B α e2 Ur = N A n − r r What is the equilibrium nearestneighbour separation r0 at which U(r0) in the above B equation is unchanged by replacing n by C exp (r/r)? r Solution: B = r nC exp( −r / ρ ) with r = r0 B C exp( −r / ρ ) i. Assume that there are no ions other than those shown in figure and that the charges on the cations and anions are + 1 and 1. U. B. rn = nrn1 = Substituting for B nrn1 = B ρC 1 ρC exp(r/ρ) exp(r/ρ) Cr n exp(r/ρ) rn nr n = with r = r0 ρ r Thus 1. a cup of black tea mixed with sufficient lemon juice twice a day keeps both the apple and the Doctor away.e. All bond lengths are equal and all bond angles are 90o. Each cation is distance ro from the central ion.Bonding in Solids and Crystal Structures and Xray Diffraction 41 N.7 r0 = nr Answer Calculate the value of the Madelung constant for the structure in the following figure.).K.. First we shall calculate the contribution to the potential energy of interactions of the six cations with the central anion. programme 1997. Solution: There are seven ions in the structure. 1.
1.42 Applied Physics Thus E1 = − 6 e2 4π ∈0 r0 Each cation also interacts with diametrically opposite cations (distance 2ro).44 eV 4πε0r0 n . n = 9.99 Answer 1. so E2 = + 3e2 4π ∈0 2r0 Finally. (JNTU.61 eV.281 nm. of an ion pair is V = Ae2 n − 1 = 7.E. ionisation energy of Na = 5. E3 is calculated from interactions between adjacent cations [distance ( 2 )r0 ] of which there are twelve.5 8.8 Calculate the cohesive energy of NaCl from the following data: r 0 = 0. Now E3 = + Thus E = E1 + E2 + E3 = − 4π ∈ r 6 − 2 − 2 0 0 e2 3 12 12e 2 4π ∈0 ( 2 )r0 = Ae2 4πε0r0 with A = 6 1. electron affinity of Cl is 3.99 A = 3.748. BE May 2002) Solution: The P. There are three such interactions.1 eV.5 = 3. A = 1.
95eV 1. a = 4r 3 with 2 atoms in an unit cell For fcc structure. a = 4r 2 with 4 atoms in an unit cell Volume of bcc unit cell per atom a3 4 r3 = = 6.K. University of Manchester. Between 273 and 912 oC iron is bcc crystal also called a iron. iron is in bcc form called d iron.158r 3 Vb = 2 3 2 Volume of fcc unit cell per atom a 3 1 4r 16r 3 = = 5 .1 Answer Explain allotropic forms of iron with ranges of temperatures. The most common example is that of iron which shows different allotropic forms at different temperatures.. 0.14 3. Between 912 and 1394oC iron is in fcc form. the energy required to make an ion pair from Na and Cl atoms.53 eV. i. B. we must add to this. Each atom therefore contributes half of 1. 5.2. U.72 + 0. These are shown in the following figure.53 i. Between 1394oC and its melting point. Solution: For bcc structure.e.95 eV. Whether any change in volume is noticed when a metal exists in more than one form? (Metallurgy division. the phenomenon is termed allotropy or isomorphism. September 1982) When an element or a compound can exist in more than one crystalline forms at different temperatures. Tech.. also known as g iron.77 eV to the cohesive energy.77 = 2..61 = 1.e. Hence the cohesive energy of NaCl/atom is thus Ec = 3.658r 3 Vf = = 4 4 2 2 2 3 3 .Bonding in Solids and Crystal Structures and Xray Diffraction 43 To calculate the cohesive energy. Ec = 2. This energy is the difference between ionisation energy of Na and electron affinity of Chlorine.
2.023 ´ 1023 /gmol as SI system is followed almost everywhere.2.02 × 10 a = 2.4 times the lattice constant of chromium (bcc) structure.86 kg/cm 3.86 gm/cm3 or 7860 kg/m3 and it is suggested to use 6.657r 3 ∆V = 0.02 × 1026/kmol 1/3 55. Compare the radii of the atoms of these metals. November 1979). there is a reduction of volume for a given mass.158 r 5. (Department of Electronic and Electrical Engineering..287 × 10 −9 metre Answer The lattice constant of aluminium (fcc) structure is 1. This must be equal to n = 2 MA ρ N A a3 n= MA Thus or with a= ρN A M An 1/3 (i) r = 7860 kg/m3 (ii) n = 2 (iii) MA = 55. . The density is 7.023 × 1023/mol. 3 3 ∆V = 6.023 ´ 1026/kmol for Avogadros number instead of 6. May 2004) Solution: This problem carries some errors. U. (Anna U.85 × 2 a= 26 7860 × 6.85 (iv) NA = 6.2 Calculate the lattice constant of iron. A ρ Thus a3 will have ρ N A a3 atom. Loughborough University of Technology.3 = 0. Given: density of iron 7. atomic weight of iron 55. the change of volume per atom is.85 and Avogadros number 6.87 nm 1.K.501 r Answer 1. MA 3 m will contain N atom.44 Applied Physics Now it is established that when bcc structure changes to fcc.
BE.4 × 1.3 0.2. Find the intercepts on the y and z axes.12 nm on the xaxis.282 nm Volume considered 80 cm 3 . US.732 Answer rA = 1.3 r 3 × 0.4 = aC rC 3 2 or rA = 1.414 rC = 1.12 nm.12 × 3 =1 = q 2 × 0.2 : : p :q : r= 2 3 1 Solution: Thus i.12 0.244 nm. a plane (2 3 1)' has an intercept of 0. Similarly.6 r= q 0. (Bangalore U. Let p. The nearest neighbour distance of this structure is 0.14rC 1.5 The toycar of Mr.2. r be the three intercepts.2 nm. then 0. q.4 nm 0.4 nm 1.18 nm and 0.4 In a crystal whose primitives are 0..12 nm. May 1982).244 = = a= 1.18 0.18 = = = 0. April 1982).732 3 3 a = 0. 0.14rC 1.12 = = 0. (University of Maryland. p 0.18 0.2 0. 8 cm and 1 cm. r = 0. he threw all the parts except the chase. It is of airon with bcc structure at 300 K and a rectangular plate with dimensions 10 cm.12nm as p = 0.e. Solution: 4r 2 × 2r 2 × 0.. Compute the number of unit cells in this specimen. Ajay was heavily damaged.18 q = p = 0.3 Answer q = 0.12 nm q 0.Bonding in Solids and Crystal Structures and Xray Diffraction 45 Solution: aA = 4rA 2 4rC 3 aC = aA rA = 1.
(Anna.98 1 m3 may contain n = 6. December 2001). JNTU.406 nm Answer a = 0.406 nm V = a3 = 6.r= a × 1.406 × 1.02 × 1028 M An (b) a = ρN A 1/3 Answer 1/3 26.57 × 1024 1.732 0. BE. U.98 3 m will contain 6.176 nm 4 4 r = 0.46 Thus (0.6 Applied Physics 80 0. (d) Find the radius of the interstitial sphere that can just fit into the void at the body centre of this fcc structure coordinated by the facial atoms.98 × 4 = 2698 × 6. BE.406 × 109 m a = 0.282 3 = 3. November 1984.2. .69 × 1029m (c) a = Answer 4r 3 . (c) Calculate the atomic radius aluminium.732 = = 0.98.02 × 10 26 = 0.69 × 1029 m3 V = 6. Solution: (a) 26.282 × 107)3 cm3 has one unit cell 80 cm3 therefore will have 3.57 × 1024 cell Aluminium has density of 2698 kg/m3.02 × 10 26 26. Calculate (a) How many atoms are contained in 1 m 3 of this metal? (b) Get the size of the unit cube for aluminium.176 nm Answer (d) Let r be the radius of the atom and R be the radius of the sphere which can just fit. Its structure is fcc and atomic weight is 26.02 × 1026 atom 2698 2698 × 6.282 × 10 Answer 3 −21 = 80 × 10 21 0.
2. September 1992) Solution: n = 1 × 10 −10 = exp ( − Eν / kBT ) N Eν = 10ln10 kBT Ev = 773 × 10 × 2.7 Answer The fraction of vacancy sites in a metal is 1 × 1010 at 500°C.5 6.02 × 10 23 = 9. US. U.414 × 0 . (University of Minnesota..176 R = 0. Calculate the distance between two adjacent cations.44 × 10 −7 Answer 1. Tech.Bonding in Solids and Crystal Structures and Xray Diffraction 47 2(r + R) = a. Sc. M.708 × 1023 gm ρ= M n ×m = with V = 1 V 1 . 1994) Solution: Mass of one molecule 58. The density of NaCl = 2.2.3031 × kB n1 = exp − N1 kB × 1273 n1 N1 = 8.414r = 0 . r + R = a/2 or R= a 4r −r = −r 2 2 2 R = r( 2 − 1 ) = 0.18 gm/cm 3.8 NaCl has an fcc structure. Given: molecular weight of NaCl is 58.5.. What will be the fraction of vacancy sites at 1000°C? (Anna.3031× kB 7730 × 2.. MidSemester B.0729 nm 1.
n = 22.7 4 43.154 nm.62 × 1021 unit cell a3 will contain 5.316 nm is obtained with a monochromatic xray beam of wavelength 0.9 D = 0..18 = mass of one molecule 9.6 Line: q° Determine the interplanar spacings and Miller indices of the reflecting planes.62 × 10 21 × a 3 = 1 unit cell 1 or or a3 = 1 5.92 × 1021 One unit cell contains 8 ions.414 or 1. 1 cm3 contains 5.178 × 1021 a = 5.92 × 10 21 21 = 5.62 × 10 8 i.3 2 29.46 × 1021 = 44.2 3 36. therefore number of unit cells in one cm3 is 44..98 × 10 −8 cm 1.398 nm Answer A diffraction pattern of a cubic crystal of lattica parameter a = 0.62 × 108 cm Cationcation distance is the face diagonal of the primitive cell a2 a a D = 2 +2 = 2 2 2 2 D = a 2 = 5.62 × 10 21 = 0. sin θ = d= sin θ d .e.e.2.48 Hence the number of molecules in 1 cm3 of NaCl is n= Applied Physics ρ 2 .626 × 10 −8 = 3. 708 × 10 −23 i.46 × 1021 molecules/cc Hence number of ions in one cm3 = 2 × 22. Solution : λ λ . The first four lines on this pattern were observed to have the following values: 1 20.
. 0. Given: a = 1.36 eV. l) one has to resort to trial and error method.3460 0. = 22 + 22 + 0.7 43. BE May 1990) 1.1570 0.19 × 10115 J m10. (Ans: 4.1290 0. The ionic radii of Cs and Cl are 0.6900 For determining (h.K.1150 a2 d 2 = h2 + k 2 + l 2 2 4 6 8 20.Bonding in Solids and Crystal Structures and Xray Diffraction 49 Line 1 2 3 4 θ sin θ d (nm) 0. (JNTU May 1997).5 respectively.81 nm and their atomic weights are 133 and 35.165 nm and 1.4 1.1 kg of chlorine to form KCl? (Ans: 20 kgatom) (a) How much energy is required to form a Li+ and Br ion pair from a pair of Li and Br pair of atoms? (b) What must be the separation between a Li+ and Br ion pair so that their total energy is to be zero. calculate the equilibrium spacing ro in terms of B and r.2240 0.71 nm) (Anna. hkl hkl hkl hkl =(110) =(200) =(211) =(220) EXERCISE 1. (Ans: r ln B) (IIT Madras.3 How many kgatom of potassium will be required to treat with 709.4 eV and electron affinity of Br = 3.33 × 102 eV) M.1 The potential energy of a diatomic molecule is given in terms of the interatomic density r by the expression U (r ) = − the two atoms and the dissociation energy. k.37 × 103 kg/m3) Assuming an overlap interaction between nearest neighbours of the type f (r) = B exp( r/r) where B and r are constants. May 1992).4886 0. BE May 1990) a b + 10 . U.2 36.3 29. = 22 + 0 + 0. Calculate the equilibrium spacing of 2 r r 1. Parttime BE.5980 0.04 eV. Calculate the density of CsCl. U. (Ans: 0.2 1.0 0. h2 + k2 + l2 = 2 h2 + k2 + l2 = 4 h2 + k2 + l2 = 6 h2 + k2 + l2 = 8 = 12 + 12 + 0.047 nm.5 . 4.44 × 10 39 J m 2 and b = 2. Given: the ionisation energy of Li = 5. = 2 2 + 12 + 12 . (Ans: 2.
determine whether a gaseous molecule A+ B with respect to the separated A and B gaseous atoms: First ionisation energy of A = 500 kJ/mol Electron affinity for B atom = 335 kJ/mol Interionic separation = 0. (Ans: 1.4 1. the number of atoms per unit area of a lattice plane) in (1 0 0) and (1 1 0) planes of a bcc crystal having a as its lattice constant. BE. (AMIE. (Ans: 1. 2 / a 2 ) How is the distance between two planes of same indices calculated? Calculate the ratio of the distances of the planes with Miller indices (1 1 1) and that with Miller indices (1 0 2) in lead crystallizes in fcc structure.75 × 108) A gold smith used to prepare samples by adding 20 cc of copper in 80 cc of pure gold every time for making ornaments.1 Applied Physics Calculate the atomic density (i.8 × 1021. airon has bcc structure.7×1023m.e.E.2 1. September 1988) (Ans: 1/a2.1605 nm.. Compute the number of sodium ions and the number of unit cells if the lattice constant is 0. (Anna U. Given : Copper takes fcc structure with a lattice constant of 0. B. B.2.2.72 × 1013. 5.7 The lattice constant of the unit cell of a.2.7×1021) Copper has fcc structure and its atomic radius is 0.3 nm (Ans: 297 kJ/mol) 1. The radius of magnesium atom is 0..5 cm prepared as per the above ratio. Also compute the number of copper atoms present.9 × 103 kg/m 3) Given the following data.9 . (Ans: 22.E.iron is 0.36 nm. (Ans: 3.56 nm.8×1023) 1. Once he had a wire of 200 cm with a uniform diameter 0.2. (M. Find out the number of unit cells in copper that is added to draw the wire. Mithila a seventh standard student geometrically prepared a cube of common salt as her project work in the junior school level.4 × 1028 m 3) Miss. (The Open University.11 × 1013) 1.287 nm..3) Magnesium has hcp structure. Find the number of atoms/ mm2 of the planes (1 1 0) and (1 1 1).8 Calculate the ratio of the number of vacancies in equilibrium at 300 K in aluminium to that produced by rapid quenching at 800 K..128 nm.2. November 1992) (Ans: d1/d2 = 1.6 will be stable 1.2. 2. (Anna U. Calculate the density of copper if its atomic weight is 63. Calculate the volume of unit cell of magnesium. May 1989 and JNTU June 2004) (Ans: 8. Enthalpy of formation of vacancies in aluminium is 68 kJ/mol. (GATE 1995) (Ans: 1. When it was shown to me I found that it is a cube of NaCl with 1 cm edge.174 nm.U.2. November 1992).2. UK)..3 1.50 1. 6.5 1.5. Given radius of lead atom 0.2.
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