CRYSTALLOGRAPHY

Crystalline solids: They are incompressible, rigid with characteristic shape. The particles are arranged in a definite pattern in three
dimensional network in long range order. Eg, NaCl, Sulphur

Amorphous solids: These are rigid, incompressible to some extent but donot have definite geometrical shape. Eg: Glass, Rubber,
Plastics.

Crystalline solid Amorphous solid

1. It has definite and regular geometry. 1. It has no definite and regular geometry.

2. It has long range order. 2. It has short range order.

3. It has sharp melting point. 3. It has no sharp melting point.

4. The properties such as electrical conductivity, thermal 4. It is isotropic.
conductivity, mechanical strength and refractive index are
different in different directions, i.e. it is anisotropic.

Microcrystalline solids: Solids in which crystals are so small and can be observed only under a powerful microscope are called
microcrystalline solids. The size of crystal j depends on the rate of its formation.

Interfacial angle (law of constancy of interfacial angles): The angle between any two faces is interfacial angles. Jt is constant for a
particular crystal irrespective of the size and shape of crystal.

Interfacial angle is measured by Goniometer.

Elements of symmetry in crystal systems:

1) Plane of symmetry: It is an imaginary plane which bisects object or crystal into two equal parts such that one part is mirror
image of other part.

2) Axis of symmetry: It is a line about which the crystal can be rotated through an angle to appear more than once revolution (i.e.
rotation through an angle of 360°). If the original appearance is repeated after an angle of I80o , the axis is called "Two fold axis". If
the original appearance is repeated after an angle of 120o , the axis is called "Three fold axis". In general, if the same appearance of a
crystal is repeated on rotating through an angle of (360° /n), around an imaginary axis, the axis is called "n-fold axis".

3) Centre of symmetry: It is a point through which any line drawn intersects the surface of the crystal at equal distance in both
sections. A crystal may have any number of planes of symmetry or axes of symmetry, but it has only one centre of symmetry.
The total number of elements of symmetry in cubic crystal is:

Planes of symmetry: 3 + 6=9 elements. .

Axes of symmetry: 3 -r 4 +6 = 13 elements.

Centre of symmetry: 1 element.

Total number of elements of symmetry = 23 elements.

Law of Rational indices: “Intercepts of any face of a crystal along the crystallographic axes are either equal to the unit intercepts (a,
b, c) or whole number multiples of them.”

Miller indices and Weiss indices: The co-efficients of unit intercepts a, b and c are called Weiss indices and characterize the given set
of parallel and equidistant planes in the Weiss system of indexing the planes.
Eg, Crystal axes (3a, 2b, c), then Weiss indices are (3, 2, 1).

Miller indices are a set of integers (h, k, l) used to describe a given plane in a crystal. The Miller indices of a face of crystal are
inversely proportional to the intercepts of that face on the various axes.

Determination of miller indices for a plane:

Prepare a three-column tabic with the unit cell axes at the tops of the columns.

Enter in each column the intercept (as multiples of a, b and c) of the plane with three axes.

Invert all numbers.

Clear fractions to obtain h, k and 1 (multiply all numbers by LCD to get.whole number). The appearance of co in the Weiss system is
rather inconvenient and is avoided in Miller system of

indexing the lattice planes.

Eg: 1. Lattice plane is ( a, b, co). •

Weiss indices are 1, 1, co.

Miller indices are : (j) : Q;)

1:1:0 •

Miller indices are (1, 1, 0).

2. Lattice plane is (3a, 2b, c).

Weiss indices are 3, 2. 1.

Miller indiccs are @ : © : © ( Here LCD is 6 thus multiply by 6 to get Miller indices).

Miller indices are (2, 3, 1).

Lattice plane is (2a, -3b, ~3c).

Weiss indices are 2, -3, -o.--

. . (z£\ ■ (—] ( Here LCD is 6 thus multiply by 6 to get Miller indices).

Miller indices aie • V 3 7 'A 3 /

= (3L-2,-2).

Miller i'^^g^^vMiUer indices is indicated by placing bar on the integer], '

Lattice plane is (2a, 3b coc).

Weiss indices are 2, 3, . .

• * dices are (")'• (j) : (m) ^ ^ere ^ ^1US by 6 t0 Set Miller indices).

Millet in =2(3i2,30). " ■

Miller indices are (3.2,. °) '

Lattice plane is (a, -2b, 2c). . . . Weiss indices are 4, -2, 2. .

"ller indices are : Qj ( Here LCD is 6 thus multiply by 6 to get Miller indices).
Ml ^ . =0,-3,3). 2 Miller indices are (1,3, 3)

T ttice p^nes m cubic crystals:

A cubic system is the simplest type of crystal system where the intercepts on the three axes are equal j ' il the angles are equal to
90°. in the primitive cubic lattice, the lattice points are present at each aU ner cU^e' P^anes that can pass through the lattice
points have Miller indices (100). (110)

c-(1 ] l) (Fig"* (100) planes have intercepts only on X-axis but are parallel to Y and Z axes. The
other planes (110) have intercepts to X and \ perpendicular distance between the adjacent planes is kno

'■aTesU,T(Tn) inlcrccptrto X, Y ;mri/ ,'r-j ;« known as interplanar spacing ana denoteu l.y dhll

Fig-15.7a. (Simple cubic lattice). ' . . .

For (100) plane d|,ki = dtoo = a where 'a' is the side of cube. The spacing between/HO) planes i.e. di10 is the one half of the diagonal
of the square base of the cube (Fig- 15.5a).

Hence, di io

For plane (111), dm is calci _

cube dividing it into three equal parts. .

Body diagonal of the cube = (aV2)2 + a2 = aV3.

Hence d,„ = [^] = [^J. .

The ratio of interplanar spacing d [oo: duo : dm = a : j^=j :• [y=]^

Am- &

In face centred cubic lattice (fee), the points are .present ~at the centres of each face in addition to those at the corners of the
primitive cubic lattice. Hence parallel planes can be drawn midway between (100) and (110) planes in the primitive cubic lattice (Fig-
15.7H). The Miller indices of these planes are (200), (220) and the inter planar spacing is .

d20° = [§] and -d220 = [i7f]-

iC

n
o

' \? K\
< 5 \N; o iV
 cKN
\N \ x'" v\
1X•
*
' • Fig-15.7b (face centred cubic lattice)

Points on faces of the cube are contained ir! (Ill) planes of the simple cubic lattice and therefore additional planes are required. •
..

In body centred cubic lattice (bcc), additional points are present at ♦ r , u- i ture As

seen from Fig-15.7e, parallel planes with Miller indices (200) can he T , T\00}

Planes (222) planes can be drawn halfway between (100) p,^t"''TI'ce » additional plane is required in (110) planes as the body
centred . ■ slmPle cubic ^

interplanar spacing between d20„ and d222 is S "ed pomt ,s contained in this plane. '

daoo=[|] fe-yy. •
\*n\ = 'a
L2j .71
"
.
 Fig-15.7c (body centred cubic lattice).

Xlieratio of d|lki for different cubic lattices is shown in table-15.2. Table-15.2:

Ratio of dhki for cubic lattices.

giniplecubie lattice . cjuo . ^n( _ | 1

= 1 : 0.707 : 0.577

fee cubic lattice ll • 1 .2V3 ti 1 = 1 : 0.707 : 1.154

*200:•d22o
u220'.dm ~
1
bec cubic lattice I200 • duo '• d222 ~~ lv! = 1 : 1.414 : 0.577
?.4l
l~f2
In general the interplanar spacing d^i between the planes hkl in a cubic lattice is given by

4kl: where a = side of cube.

Vh2+ k2 + l2

Eg: Determine the interplanar spacing between (221) planes of,a cubic lattice of length 4.5A .

4.5

dhki -

\/h2+ k2+12 V22+22+ .....

Space lattice and unit cell: t1 . aria Hpcmmtprl

The positions of atoms, molecules or ions in a crystal relative to one another usually by points. This is called space lattice. It
is an array of pomts showmg how atoms 01 molecules o. ions are arranged at different sites in three dimensional space.

p
\*r
. in a three dimensional space lattice is shown in Fig-13.8. Each
point An example Fig-15.8 of array 01 P01^ moiecules. Lattice points can be
broken down into a number of unit cells. represents an identical eatjnCT unit
in space lattice which when repeated over and over again

i""!' «" of given substance. It represents the picture of entire crystal. Thus the crystal

results in a. crysta of unit cells. Each unit cell in a three dimensional space has evidently three

consists of infinite ^

Vectors a, b and c t indicates how particles are arranged in a crystal lattice. In order to describe a unit The lines joining P°J
 cell we shoul °nceS a? b and c which give the lengths of the edges of unit cell.

Ca)- T w m.

oles a, P and 7 which give the angles between the three imaginary axes. By knowing the

(b)- ^dimensions, the theoretical density of a crystal can be calculated from the relation - unitcel nMn

P ~ K1 ,, n = Number of atoms in a unit cell

N0V
fjittices:
M„ Molar mass, V - Volume of unit cell, No = Avogadro number.

Br 1.5 A1

biavais (184S) showed geometrical consideratiot similar points can be arranged in a three dimensional space

avais lattices depending upon the shape of unit ceil.

The cubic system crystals have three kinds of bra\

Simple cubic lattice or primitive cubic lattice: There are (Fig-15-9.a). . . ■, " ,, . I

Body centred cubic lattice (bcc): In addition to points at the comers of each unit cell, one point is|

present in the centre of the body (Fis-l 5-9.b). . - . • . -' c . c

3: Face centred cubic lattice (fee): There are points at corners and 6 points in the cen le of six faces of

unit cell (Fig-15-9.c).

Fig-15.9. ,

^.Calculation of number of lattice points contained in a unit cell of cubic systems:

Primitive cubic lattice: It contains S lattice points at 8 corners. Each lattice point is shared by 8 unit cells. . . ' ;

Hence number of lattice points / unit cell = S x ^ = 1 lattice point. ■:.;■■■■

bcc lattice: It consists of 8 lattice points at 8 corners of cube" and one lattice point at centre of unit cell.

Hence number of lattice points / unit cell = 8x^ +. .1 = 2 lattice points.

3. fee lattice: It consists of 8 lattice points at 8;corners of cube and 6 lattice points at 6 faces. These are shared by 2 unit cells.
.

Hence number of lattice points / unit cell = 8 x ^ + 6 x '/2 =4 lattice points.

X-ray diffraction and Bragg's equation:

Crystal undergo diffraction by X-rays since wavelength of X-ray is of about the same order of inter atomic distances
in a crystal. From diffraction pattern, it is possible to find size, shape and the detailed information regarding the
position of atoms in a crystal.
Bragg's equation: Crystals consist of a large number of parallel and equidistant atomic planes. Diffraction effects
are represented as reflection by successive planes. When X-rays are incident on a crystal face they penetrate into
the crystal and are scattered by the atoms or ions.

Consider a set of parallel and equidistant planes AA, BB, CC etc., in a crystal. A beam of X-ray of wavelength 
strikes these planes at an angle of 𝜃. Some of these rays will be reflected by atoms from the upper layer AA with an
angle of reflection same as angle of incidence 𝜃. Some of the rays will be absorbed and some will be reflected from
second layer and so on with successive layers. When the rays reflected from the successive layers are in phase,
constructive interference will occur and a bright diffraction spot obtained from these planes.

The condition for the constructive interference is that the path difference between the reflected rays from
successive planes must be an integral multiple of wavelength.

The path difference for KOP and QNR = LN + MN

 n = LN + MN
Since the triangles OLN and ONM are congruent LN=MN

n = 2 LN -----------------------------------------(1)

𝐿𝑁
Triangle OLN is right angled triangle, sin𝜃 = 𝑂𝑁

LN = ON sin 𝜃 (But ON = d)

LN = d sin 𝜃 ----------------(2)

Put Eq (2) in (1)

This is Bragg equation.

If n =1 order of reflection is one, n=2 order of reflection is two………..

 is known, 𝜃 is determined experimentally and hence interplanar distance d can be calculated.

Determination of crystal structure of rock salt by rotating crystal method using Bragg's spectrometer.
X-ray spectrometer designed by W.H.Bragg (1913) is used for interpretation of crystal structure.

X-rays produced in the X-ray tube is passed to strike a single crystal (C) mounted on rotating table. The crystal is
rotated gradually so as to increase the glancing angle at which the X-rays are incident. The intensities of the
reflected rays are measured using recording device. The angle for which reflection is maximum, gives 𝜃. The
process is carried out for each plane of the crystal. The lowest angle at which the maximum reflection occurs
corresponds to n=1. This is called first order reflection. The next higher angle at which the maximum reflection
occurs, corresponds to n=2, called second order reflection and so on.
The values of 𝜃 for the first order reflection from three faces of crystal are 5.9°, 8.4° and 5.2° respectively. Using
Bragg s equation, the distance d between successive planes in three faces will be in the ratio of (since n=1 and  is
fixed)
 This ratio is very close to spacing between the three planes of fcc cubic lattice. Therefore NaCl crystal has fcc
cubic structure.

Liquid crystals (Mesomorphic state): There are certain solids on heating undergo two sharp transformations.
1. They fuse sharply giving turbid liquid.
2. Then at higher temperature, they give clear liquid.
These changes are exactly reversed on cooling. The turbid liquid show anisotropy (different physical properties in
different directions particularly optical property). True liquid is isotropic (physical properties are same in all
directions). Turbid liquids show double refraction and interference which are characteristic property of crystals.
Turbid liquid is called "liquid crystal"("mesomeric state"). Liquid crystals obtained by heating or cooling are called
theromotropic liquid crystals. They do not have the properties of crystalline state but they are more like liquids.
Substances like long chain organic molecules either terminating in groups like -OR, - COOR or having groups like -CN,
-N = N-, -C = C- in the middle show above behaviour. Eg: Cholesteryl benzoate was the first solid discovered (1888) to
have this property. It fuses sharply at 145°C to give a turbid liquid and at 178°C it changes into clear liquid.
The temperature at which turbid liquid is formed is called transition point (Tp) and the
temperature at which clear solution is obtained is called melting point (MP). The substances
showing liquid crystal character is highly stable and do not decompose on heating.