Solid State

Solid State
Gases and liquids can f low and take up the shape of
their
container. Solids, on the other hand, have a def in ite
volume and shape. They are rigid and lack the ability
to flow.
The atoms, ions and molecules are held together by
relatively strong chemical forces-
• ionic bond,
• covalent bond, or
• intermolecular van der Waals’ forces.
They do not translate although they vibrate to some
extent in their fixed positions. This explains why solids
are rigid and have definite shape.
Cont’d
 Solid State Chemistry
Solid-state in Chemistry is the study of the structure,
properties and synthesis of solid materials. It is also
so m eti m es cal l ed m ater i al s c hem i str y . M o re
signif ic antly, in solid-state chemistry, we study the
concept of a compound on a deeper level. It basically
helps us understand the compound from a molecular
level to a crystal structure level.
In solid-state chemistry, nonstoichiometric compounds
are categorised as exclusive solid-state compounds due
to their structure and thermodynamics characteristics.
Cont’d
 Physical and Chemical Properties of Solids
 Solids are incompressible, which means the constituent
particle is arranged close to each other and because of that,
there is negligible space between the constituent particle.
 Solids are rigid. This is due to the lack of space between the
constituent particles, which makes it rigid or fixed.
 Solids have definite mass, volume and shape, due to which it
has a compact arrangement of constituent particles.
 The intermolecular distance between molecules is short.
Due to this, the force between the constituent particles
(atoms, molecules or ions) is very strong.
 The constituents particles can only oscillate about their
mean positions.
TYPES OF SOLIDS
 Broadly speaking, solids are of two types :
 (a) Crystalline solids; also called true solids
 (b) Amorphous solids
A crystalline solid exists as small crystals, each crystal
having a characteristic geometrical shape. In a crystal,
the atoms, molecules or ions are arranged in a regular,
repeating three-dimensional pattern called the crystal
lattice. Sugar and salt are crystalline solids.
Cont’d
 Properties of Crystalline Solids
 Crystalline solids have a sharp melting point and start melting
when it reaches a particular temperature.
 The shape of crystalline solids is definite and has typical
arrangements of particles.
 They show cleavage property, i.e., when they are cut with the
edge of a sharp tool, they split into two pieces, and the newly
generated surfaces are smooth and plain.
 They have definite heat of fusion (amount of energy needed to
melt a given mass of solid at its melting point).
 Crystalline solids are anisotropic, which means their physical
properties, like electrical resistance or refractive index, show
different values when they are measured along with different
directions in the same crystal.
 Crystalline solids are true solids.
Cont’d
 Types of Crystalline Solids
 On the basis of the nature of intermolecular forces or
chemical bonding, crystalline solids are further
classified into four categories. They are as follows:
 Molecular solids
 Ionic solids
 Metallic solids
 Covalent solids
Cont’d
 A. Molecular Solids
 I n mole cular solids, th e con stitue n t particle s are
molecules. They are further divided into three categories:
 1. Non-polar Molecular Solids
 These solids are formed from molecules or atoms that
share a non-polar covalent bond. The atoms or molecules
are held by weak dispersion force or by London forces.
 The physical nature of non-polar solids is soft.
 They don’t conduct electricity, so they are insulators.
 They have a very low melting point.
 Examples: H , Cl , I etc.
2 2 2
Cont’d
 2. Polar Molecular Solids
 These solids are held together by polar covalent
bonds, and the atoms/molecules are bonded by
relatively stronger dipole-dipole interactions.
 The physical nature is soft, and most of these are
gases or liquids at room temperature.
 They do not conduct electricity, and they have a
higher melting point than non-polar molecular
solids.
 Examples: HCl, SO2, NH3, etc.
Cont’d
 3. Hydrogen-bonded Molecular Solids
 The solids contain polar covalent bonds with Hydrogen,
Fluorine, Oxygen and Nitrogen atoms. Molecules are
held together via strong hydrogen bonding.
 The physical nature of such solids is hard.
 They do not conduct electricity.
 The physical state of these solids is volatile liquids or
soft solids under room temperature.
 They have a low melting point.
 Example: H2O (Ice ).
Polar Covalent Bond in H2O
Cont’d
 B. Ionic Solids
 In ionic solids, the constituent particles are ions.
These are formed by the arrangement of cations and
anions by strong Coulombic forces.
 These are hard and brittle in nature.
 Ionic solids act as an insulator in a solid-state but are
conductors in a molten and aqueous state.
 They have a high melting point.
 Examples: NaCl, MgO, ZnS, CaF2 etc.
Cont’d
 C. Metallic Solids
 Positive metal ions in a sea of delocalised electrons.
These electrons are evenly spread out throughout
the crystal.
 Due to the presence of free and mobile electrons,
they are responsible for high electrical and thermal
conductivity.
 They are conductors in both solid and molten states.
 The physical nature of these solids is hard, but they
are malleable and ductile.
 They have high melting point than ionic solids.
 Examples: Fe, Cu, Ag, Mg, etc.
Cont’d
 D. Covalent or Network Solids
 A wide range of crystalline solids of non-metal form
covalent bonds between adjacent atoms throughout
the crystal and form giant molecules or large
molecules.
 These solids are hard, like diamond and soft, like
graphite which are isotopes of carbon.
 They are insulators, as in the case of a diamond, but
in the case of graphite, due to free electrons, they
conduct electricity and act as a conductor.
Amorphous solid
 An amorphous solid (Gr amorphous = no form) has
atoms, molecules or ions arranged at random and
lacks the ordered crystalline lattice. Examples are
rubber, plastics and glass. In their disordered
structure, amorphous solids resemble liquids. Thus
glasses are to be regarded as super-cooled or highly
viscous liquids.
Cont’d
 Properties of Amorphous Solids
 Amorphous solids are gradually softened over a range of temperatures,
and they can be moulded into different shapes on heating.
 Amorphous solids are pseudo-solids or supercooled liquids, which
means they have a tendency to f low very slowly. If you observe the glass
pans, which are f ixed to windows of old buildings, they are found to be
slightly thicker from the bottom than at the top.
 Amorphous solids have irregular shapes. i.e., their constituent particles
do not have definite geometry of arrangements.
 When amorphous solids are cut with a sharp edge tool, they form pieces
with irregular surfaces.
 Amorphous solids do not have definite heat of fusion due to the irregular
arrangement of the particles.
 Amorphous solids are isotropic in nature, which means the value of any
physical property would be the same along any direction because of the
irregular arrangement of particles.
ISOTROPY AND ANISOTROPY
 Isotropy: Property of a material being uniform in all
directions.
 Physical properties remain consistent regardless of the
measurement direction.
 Example: Glass
 Refractive index and mechanical strength are uniform in
all directions.
 Anisotropy: Property of a material exhibiting different
values in different directions.
 Properties vary based on crystallographic directions.
 Example: Mica (silicate mineral crystal)
 Cleavage planes lead to different properties along and
perpendicular to the sheets.
Anisotropy in Crystalline Solids
 Crystal l i ne substances are ani so tro pi c and the
magnitude of a physical property varies with directions.
 Fo r exa m p l e, i n a c r y sta l o f si l v er i o d i d e, the
coeff ic ient of thermal expansion is positive in one
direction and negative in the other.
 Similarly, velocity of light in a crystal may vary with
direction in which it is measured. Thus a ray of light
passing through a Nicol prism (made from calcite
crystal) splits up into two components, each travelling
with different velocity (double refraction).
Isotropy in Amorphous Solids
 Amorphous substances are said to be isotropic
because they exhibit the same value of any property
in all directions. Thus refractive index, thermal and
electrical conductivities, coeff ic ient of thermal
expansion in amorphous solids are independent of
the direction along which they are measured.
 Amorphous solids are useful materials. Glass, rubber
and plastics find many applications in our daily lives.
Amorphous silicon is one of the best photovoltaic
material available for conversion of sunlight into
electricity.
THE HABIT OF A CRYSTAL
The external shape is called the habit of the crystal. The plane surfaces of
the crystal are called faces. The angles between the faces are referred to as
the interfacial angles. The interfacial angles for a given crystalline
substance are always the same.
 Consistency in Interfacial Angles:
 Interfacial angles remain constant for a given crystalline substance.
 Crystal Growth and Habit:
 Habit depends on the rate of development of different faces.
 Slow growth from a slightly super-saturated solution or slow cooling
results in large crystals.
 Variability in Crystal Appearance:
 Crystals of the same substance may appear different.
 Presence of impurities affects face growth rates, leading to various forms.
 Example of Impurity Influence:
 Sodium chloride crystallizes into cubic crystals.
 Addition of urea as an impurity results in octahedral crystals.
SYMMETRY OF CRYSTALS
 Symmetry in crystals may be due to
a plane, a line or a point. There are
three types of symmetry elements
associated with a crystal. These are
called the Elements of Symmetry.
 (1) Plane of Symmetry
 A crystal is said to have a plane of
symmetry if it can be divided by an
imaginary plane into two equal parts,
each of which is the exact mirror
image of the other.
Cont’d
 (2) Axis of Symmetry
A n a x i s o f s y m m e t r y i s a n
imaginary line drawn through the
crystal such that during rotation
of the crystal through 360º, the
crystal presents exactly the same
appearance more than once. If
similar view appears twice, it is
called an axis of two fold
symmetry or d iad axis. If it
appears thrice, it is an axis of
three old symmetry or triad axis,
and so on.
Cont’d
 (3) Centre of Symmetry
 It is a point at the centre of the
crystal so that any l i ne drawn
through it will meet the surface of
the crystal at equal distances on
either side.
 It is noteworthy that a crystal may
have a number of planes of
symmetry or axis of symmetry but
i t can have o nly o ne centre o f
symmetry.
CRYSTAL STRUCTURE
•The particles (atoms, ions or molecules) in crystals are
highly ordered as is evident from their geometrical
shapes, smooth surfaces and specific interfacial angles.
•The particles in crystals are arranged in regular
patterns that extend in all directions. The overall
arrangement of particles in a crystal is called the
Crystal lattice, Space lattice or Simply lattice.
Cont’d
 The simple basic unit or the building block of the
crystal lattice is called the Unit cell.
How to Represent Crystal Lattice and Units
Cells?
T h e c r y s t a l l a t t i c e o f a
s u b s t an ce i s d e p i cte d b y
showing the position of
particles (structural units) in
space. These positions are
represented by bold dots (or
circles) and are referred to as
lattice points or lattice sites.
The overall shape and
structure of a crystal system
is governed by that of the
unit cell of which it is
composed.
Cont’d
 There are only 14 possible three dimensional lattices.
These are called Bravais Lattices (after the French
m athem ati c i an who f ir st desc r i bed them). The
following are the characteristics of a crystal lattice:
 (a) Each point in a lattice is called lattice point or
lattice site.
 (b) Each point in a crystal lattice represents one
constituent particle which may be an atom, a molecule
(group of atoms) or an ion.
 (c) Lattice points are joined by straight lines to bring
out the geometry of the lattice.
Cont’d
 Unit cell is the smallest portion of a crystal lattice which, when
repeated in different directions, generates the entire lattice.
 A unit cell is characterised by:
 (i) its dimensions along the three edges, a, b and c. These edges
may or may not be mutually perpendicular.
 (ii) angles between the edges, α (between b and c) β (between a
and c) and γ (between a and b).
Primitive and Centred Unit Cells
Unit cells can be broadly divided into two categories,
primitive and centred unit cells.
 (a) Primitive Unit Cells
When constituent particles are present only on the
corner positions of a unit cell, it is called as primitive
unit cell.
 (b) Centred Unit Cells
When a unit cell contains one or more constituent
particles present at positions other than corners in
addition to those at corners, it is called a centred unit
cell.
Cont’d
 Centred unit cells are of three types:
 i) Body-Centred Unit Cells: Such a unit cell contains one
constituent particle (atom, molecule or ion) at its body-
centre besides the ones that are at its corners.
 ii) Face-Centred Unit Cells: Such a unit cell contains one
constituent particle present at the centre of each face,
besides the ones that are at its corners.
 iii) End-Centred Unit Cells: In such a unit cell, one
constituent particle is present at the centre of any two
opposite faces besides the ones present at its corners.
Primitive cubic unit cell
 Primitive cubic unit cell has atoms only at its corner.
Each atom at a corner is shared between eight
adjacent unit cells as shown in Fig. 1.8, four unit
cells in the same layer and four unit cells of the
upper (or lower) layer. Therefore, only 1/8 of an atom
th

(or molecule or ion) actually belongs to a particular

unit cell. In Fig. 1.9, a primitive cubic unit cell has
been depicted in three different ways. Each small
sphere in Fig. 1.9 (a) represents only the centre of
the particle occupying that position and not its
act u al s i ze . Su ch s t ru ct u re s are cal le d op e n
structures. The arrangement of particles is easier to
follow in open structures.
Cont’d
 Fig. 1.9 (b) depicts space-filling representation of the
unit cell with actual particle size and Fig. 1.9 (c)
shows the actual portions of different atoms present
in a cubic unit cell. In all, since each cubic unit cell
has 8 atoms on its corners, the total number of
atoms in one unit cell is 8 X 1/8 = 1 atom.
Body-centred cubic unit cell
 A body-centred cubic (bcc) unit cell has an atom at
each of its corners and also one atom at its body
centre. Fig. 1.10 depicts (a) open structure (b) space
f il ling model and (c) the unit cell with portions of
atoms actually belonging to it. It can be seen that
the atom at the body centre wholly belongs to the
unit cell in which it is present.
Cont’d
 Thus in a body-centered cubic (bcc) unit cell:
Face-centred cubic unit cell
 A face-centred cubic (fcc) unit cell contains atoms at
all the corners and at the centre of all the faces of
the cube. It can be seen in Fig. 1.11 that each atom
located at the face-centre is shared between two
adjacent unit cells and only 1/2 of each atom
belongs to a unit cell. Fig. 1.12 depicts (a) open
structure (b) space-filling model and (c) the unit cell
with portions of atoms actually belonging to it.
Cont’d
 Thus, in a face-centred cubic (fcc) unit cell: