MODULE 1

CRYSTAL STRUCTURE AND PHASE RULE

Crystal Structure:
1. Crystalline solids: In crystalline solids the building constituents (atoms, ions or molecules)
arrange themselves in a three dimensional recurring regular geometric pattern. Crystalline
solids exist as crystals and hence these are also called simply crystals. A crystalline solid has
a sharp melting point.

2. Amorphous solids: The word amorphous is a Greek word which means shapeless. Thus, in
these solids the arrangement of different building constituents is not regular but haphazard i.e.
the constituents are arranged at random in the same disorderly way as in liquids. An amorphous
substance does not have a sharp melting point.

Types of Symmetry in Crystals

1. Centre of symmetry: It is such an imaginary point within the crystal that any straight line
drawn through it will intersect the faces, edges or solid angles of the crystal at equal distances
on opposite sides. A crystal may have either one or no centre of symmetry. It can never have
more than one centre of symmetry. A cubical crystal like NaCl crystal has one centre of
symmetry as shown in Fig. 1.

Fig. 1. Centre of symmetry in a cubical crystal.

2. Axis of symmetry: It is an imaginary straight line about which., if the crystal is rotated, it
will present the same appearance more than once during its complete rotation. There are
thirteen axes of symmetry possessed by a cubical crystal like NaCl as shown below

(a) Six axes of two-fold symmetry. Each of these six axes is called diad axis. When the crystal
is rotated about any of these axes, it presents the same appearance two times in a complete
rotation (Fig. 2A). Each of these three axes intersects at the middle points of the two opposite
edges of the cube.

(b) Four axes of three-fold symmetry. Each of these axes is called triad axis. When the crystal
is rotated about any of these axes, it presents the same appearance three times in a complete
rotation (Fig. 2B). Each of these four axes intersects at the two opposite solid angles of the
cube.

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c) Three axes of four-fold symmetry. Each of these three axes is called tetrad axis. When the
crystal is rotated about any of these axes, it presents the same appearance four times in a
complete rotation (Fig. 2C). Each of these three axes intersects at the middle points of the two
opposite faces of a cube. All the three axes are at right angles to one another.

Fig. 2. Axes of symmetry in a cubical crystal.

3. Plane of symmetry: It is an imaginary plane which divides a crystal into two such parts
that one is the exact mirror image of the other. In other words, a plane of symmetry divides the
crystal into two identical and similarly placed halves. There are nine planes of symmetry
possessed by a cubical crystal like NaCl as shown below

(a) Three rectangular planes of symmetry. One such rectangular plane of symmetry is shown
in Fig. 3A. There are in all three such rectangular planes of symmetry which are at right angles
to each other.
(b) Six diagonal planes of symmetry. One such diagonal plane of symmetry is shown in Fig.
3B. There are in all six such diagonal planes of symmetry which pass diagonally through the
cube.

Fig. 3. Planes of symmetry in a cubical crystal.

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Crystal Lattice and Unit Cell:

In crystals, the constituent particles are represented by points. These points are called lattice
points or lattice sites and the arrangement of points in the crystal is called crystal lattice or
simply crystal. Crystal lattice is also called by other names like space lattice or lattice array.
Thus a crystal lattice can be defined as follows.

A crystal lattice is an array of points which show how the constituent particles (atoms, ions or
molecules) of a crystal are arranged at different sites in three dimensional space.

The crystal lattice is actually composed of many small parts of the lattice. This smallest part
has all the characteristic features of the entire crystal and is called unit cell. Thus, a unit cell
of a crystal lattice can be defined as “A unit cell is the smallest sample that represents the
picture or definite pattern of the entire crystal”.

Fig. 4. Crystal lattice and unit cell.

The internal structure of crystals (i.e. the arrangement of the particles viz. atoms, molecules or
ions of which the crystal is composed) can be determined by X-ray diffraction, electron
diffraction, neutron diffraction etc. methods.

Crystal Systems:

Depending on the nature of the constituents (which may be atoms, molecules or ions) of which
a given crystal is composed, we have different types of crystal. The shape of a given crystal
can be described by the lengths of the three sides or edges (a, b and c) of its unit cell and the
three angles (α, β, and γ) between the three axes of the unit cell. The lengths of the sides of the
unit cell are called primitives or crystal axes and the angles between the three axes are called
interfacial angles. There are seven crystal systems corresponding to the seven distinct types of
unit cells (sub-units) (Table 1).

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Table 1. Seven systems of crystals

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From the above table the following points may be noted
(i) For cubic and trigonal systems, the three edges are of equal lengths while for the remaining
five systems the edges are not equal.
(ii) All the three interfacial angles are of 90° for cubic, tetragonal and orthorhombic systems
while these angles for other systems are not of 90º.

Types of Crystals:
Based on the nature of the building particles occupying the lattice points (or lattice sites) in the
crystal lattice and the nature of the bonds existing between the building particles, crystals can
be classified into four types.

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1. Ionic crystals. Ionic crystals are those crystals in which the particles forming the crystal are
positively and negatively charged ions (i.e. cations and anions) which are held together by
strong electrostatic force of attraction (i.e. by ionic bonds). Examples, NaCl, CuSO4. 5H20 etc.

2. Metallic crystals. Metallic crystals are those in which the particles forming the crystals are
metallic positive ions (called positive cores or Kernels) which are surrounded by a sea of
electrons (also called electron-gas or electron-cloud) and are held together by metallic bond
(Fig. 5). The positive metal ions are obtained when the metal atoms lose their valence-shell
electrons. The electrons obtained from a sea of electrons. These electrons are not bond up with
any particular metal ion and hence are free to move throughout the metallic crystal. Due to
their mobile nature these electrons are called mobile or delocalised electrons. These mobile
electrons keep the metal positive ions held together.

Fig. 5. Positive cores surrounded by mobile electrons.

3. Atomic or covalent crystals. Atomic crystals are those in which the particles forming the
crystal are neutral atoms of the same element (as in diamond) or of different elements (as in
SiC) which are held together by covalent bonds. Atomic crystals are of two types
(i) Those in which atoms are bonded with each other by covalent bonds resulting in the
formation of giant molecules. Examples of giant molecules are diamond, silicon carbide (SiC).
aluminium nitride (AlN) etc.
(ii) Those which consist of separate layers. Examples of covalent crystals containing separate
layers are graphite, CdI2, CdC12, BN etc.
4. Molecular crystals. Molecular crystals are those in which the particles forming the crystal
are polar or non-polar molecules, except in solidified noble gases in which the particles are
atoms, which are held together by two types of inter-molecular forces given below.
(a) Dipole-dipole forces. These forces occur in solids which consist of polar molecules like
water molecules (in ice, or even in liquid state). In water the negative end of one molecule
attracts the positive end of the neighbouring water molecule as shown below

(b) van der Waals forces. These forces are more general and occur in all kinds of
molecular crystals.

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Comparison of the properties of different types of crystals

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X-ray diffraction (XRD):
X-rays are electromagnetic radiation with very short wavelength ( 10-8 -10-12 m). They
are produced whenever high-speed electrons collide with a metal target. In general, the particle
scatters the incident X-ray beam uniformly in all directions. In the case of crystalline material,
the scattered beam may add together in a few directions and reinforce each other to give
diffracted beams, which is called X-ray diffraction (XRD). XRD is a powerful nondestructive
technique for characterizing crystalline materials. It provides information on structures, phases,
preferred crystal orientations (texture), and other structural parameters, such as average grain
size, crystallinity, strain, and crystal defects. X-ray diffraction peaks are produced by
constructive interference of a monochromatic beam of X-rays scattered at specific angles from
each set of lattice planes in a sample. The peak intensities are determined by the distribution of
atoms within the lattice. Consequently, the X-ray diffraction pattern is the fingerprint of
periodic atomic arrangements in a given material.

XRD pattern of NaCl crystal.