Solids: A solid interface is defined as a few atomic layers that separate two solids in intimate

contact with one another, where the properties differ significantly from those of the bulk material
it separates. Solids are solid materials in which atoms, ions, or molecules arranged in a regular
repeating pattern throughout the substance, forming a crystal lattice. They exhibit distinct
properties, such as a sharp melting point and well-defined cleavage planes.

Contents:

 Physical and Chemical Properties of Solids

 Solid State Chemistry
 Types of Solid States
 Crystalline Solid State
 Amorphous Solid State

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.

Solid State Chemistry

Solid-state in Chemistry is the study of the structure, properties and synthesis of solid materials.
It is also sometimes called materials chemistry. More significantly, 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 thermodynamic characteristics.
Types of Solid States

Based on the arrangement of constituent particles, solids are classified into two-state types:

1. Crystalline Solids
2. Amorphous Solids

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Crystalline Solid State

Crystalline solids are those that have a typical geometry. In such types of solids, there are
definite arrangements of particles (atoms, molecules or ions ) throughout the 3-dimensional
network of a crystal in a long-range order. Examples include Sodium Chloride, Quartz,
Diamond, etc.

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.

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

Molecular Solids

In molecular solids, the constituent particles 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.

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  Examples: H2, Cl2, I2 etc.
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.
3. Hydrogen-bonded Molecular Solids

The solids contain polar covalent bonds with Hydrogen, Fluorine, Oxygen and Nitrogen atoms.
In these solids, 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 ).

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.

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.

Covalent or Network Solids

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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 State

Amorphous solid-state comprises those solids which have the property of rigidity and
incompressibility but to a certain extent. They do not have a definite geometrical form or long
range of order. Examples include glass, rubber, plastic, etc.

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 super cooled liquids, which means they have a
tendency to flow very slowly. If you observe the glass pans, which are fixed 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.

Amorphous Solids Uses

Amorphous silicon, which is one of the best photovoltaic materials, converts sunlight into
electricity.

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Defects in Solid: Solids are formed from many small crystals. However, during the process of
crystallization, the defect in solids occurs due to the fast or moderate rate of formation of
crystals. Defects, in general, are defined as those in which there will be irregularities in the
arrangements of constituent particles. On the basis of irregular arrangement, the defect may be a
point or line defect. In an ideal crystal, when there are any irregularities of arrangement around
any point or any atom, it is said to be a deviation point defect. Likewise, when there is any
deviation of arrangement in the entire row of lattice points of crystals, such type of defect will be
a line defect. We will learn about all types of defects in solids in this lesson.

Table of Contents

 Types of Defects in Solids Stoichiometric Defect

 Schottky Defect Frenkel Defect
 Impurity Defects Non-stoichiometric Defects
 Metal Deficiency Defect

Types of Defects in Solids

As we know, according to the third law of thermodynamics, at absolute 0 K temperature, any

substance will be perfectly crystalline, but on increasing temperature, defects in solids are
created, which are classified into the following three types:

 Stoichiometric defects
 Non-Stoichiometric defects
 Impurity Defects

Stoichiometric Defects

The defect in which the stoichiometry of the compound remains the same, as shown by their
chemical formula. It is also called an intrinsic or thermodynamic defect. They are further
classified into two types:

 Vacancy defect: (Vacant sites in the lattice)

 Interstitial defect: (Constituent particles move to the interstitial site of the lattice)
Both vacancy and interstitial defects are only for non-ionic solids. Ionic solids, which maintain
the neutrality of the crystal, are shown by Frenkel and Schottky defects.
Schottky Defects This defect occurs due to the missing of the same number of cations and
anions from the lattice site. This type of defect is shown by that substance, which has high
coordination number.

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Schottky defect generally occurs in ionic compounds in which the radius ratio of cation and
anion [r+/r–] is not far below unity. It is a kind of vacancy defect where an equal number of
cations and anions are missing but maintain the neutrality of the crystal. The density of such a
type of crystal decreases. Due to the presence of ions, this crystal can conduct electricity to a
small extent. For example, NaCl, CsCl, KCl, AgBr etc.

Frenkel Defect

In this type of defect, some cations are missing from their lattice site and occupy the interstitial
site of the lattice. This type of defect is shown by those substances which have low coordination
numbers. The closeness of like charges tends to increase the dielectric constant of the crystal.

Frenkel defect is a kind of dislocation defect or interstitial defect in which the smaller ion
generally cation dislocate from their position to occupy the interstitial site of the lattice or
crystal. The density of these types of crystals remains the same because there is no movement of
ions outside the crystal. This defect is exhibited in those ionic compounds in which the radius
ratio[r+/r–] is low. For example, ZnS, AgBr, AgI, AgCl etc. Note: AgBr shows both Frenkel and
Schottky defects.
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Frenkel and Schottky Defect

Impurity Defects

In the molten state, NACL contains a small amount of SrCl2 in the form of impurity in the
crystal. Due to the presence of SrCl2, some site of Na+ ion is occupied by Sr2+. To maintain the
neutrality of the crystal, one Sr2+ replaces two ions of Na+, and the remaining site of Na+ will be
vacant. For example, CdCl2 and AgCl.

Non-stoichiometric Defects

This defect is shown by compounds of d-block elements of the periodic table. These defects are
classified as metal excess defects, which are again of two types. They are as follows:

Metal excess defect due to anionic vacancy

When a compound has excess metal ions, if an anion is absent from the lattice site there, it
creates a void while is there occupied by an electron. This type of defect is shown by alkali metal
halides like NaCl, KCl, and LiCl.

When alkali metal halides are heated in an atmosphere of vapour of the alkali metal, anion
vacancies are created. This anion is then diffused to the surface of the crystal and combined with
newly generated metal cations. The electron is lost by the metal atom, which then diffuses the
crystal and occupies the anionic vacancy site, and forms F-centres inside the crystal. These F-
centres give different colours, like NaCl gives a yellow colour. KCl gives a violet colour, and
HCl gives pink colour.

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Metal excess defect due to the presence of interstitial cation

It is when an excess positive ion is located in the interstitial site. This type of defect is shown by
ZnO. When ZnO is heated, it loses oxygen reversibly. The excess Zn2+ ions are occupied in the
interstitial sites to for maintaining neutrality, electrons are enclosed in the neighbouring
interstitial sites. On heating, ZnO turns yellow colour by losing oxygen.

Metal Deficiency Defect

In this defect, some cations are missing from the lattice site, and to maintain its electrical
neutrality, another remaining cation increases its valency. For example, FeO, which is found
with a composition of Fe0.95 O, may actually range from Fe0.93O to Fe0.96O.

In the crystal of FeO, some Fe2+ cations are missing, and the loss of positive charge is made up
by the presence of the required number of Fe+3 ions.

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 Schottky Defect Frenkel Defect

1. Equal number of cations and anions are 1. A cation leaves the normal lattice site and
missing from the lattice sites. occupies an interstitial site.

2. Found in highly ionic compounds with high 2. Found in ionic compounds with low
coordination numbers. coordination numbers.

3. The cations and anions are of similar in size. 3. The anions are much larger in size than
cations.

4. Density of the solid remains the same.

4. Density of the solid decreases
5. Cation moves to an interstitial site.
5. Equal number of cationic and anionic vacancies
are present.

6, It is observed in alkali halides (NaCl, CsCl) etc. 6. It is observed in ZnS, AgBr, AgI, AgCl etc.

F-centres: The electron occupying holes, created by missing of anions from the lattice sites are called F-
centres. These F-centres are responsible for colour of the compound.

 The F-centers are point defects and can be readily formed in alkaline halides.
 The anionic sites accumulated by unpaired electrons are called F-centres.
 Such defects impart color to the crystals.
 The color arises from the excitation of electrons when they absorb energy from visible
light.
 F- center is a type of crystallographic defect.
 In this defect, the vacant site occurs through the missing anion is occupied by one or
more electrons, based on the charge of the missing ion in the crystal.
 Electrons that are present in this vacancy tend to absorb light in a visible spectrum in
such a way that the transparent material seems to be colored.
 An example of this crystal is NaCl.

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