INTRODUCTION TO SOLID STATE
The vast majority of solid substances like high temperature superconductors, bio compatible plastics, silicon chips, etc. are destined to play an ever expanding role in future development of science.
We are mostly surrounded by solids and we use them more often than liquids and gases. For different applications we need solids with widely different properties. These properties depend upon the nature of constituent particles and the binding forces operating between them. Therefore, study of the structure of solids is important. The correlation between structure and properties helps in discovering new solid materials with desired properties like high temperature superconductors, magnetic materials, biodegradable polymers for packaging, bio compliant solids for surgical implants, etc.
From our earlier studies, we know that liquids and gases are called fluids because of their ability to flow. The fluidity in both of these states is due to the fact that the molecules are free to move about. On the contrary, the constituent particles in solids have fixed positions and can only oscillate about their mean positions. This explains the rigidity in solids. In crystalline solids, the constituent particles are arranged in regular patterns.
In this Unit, we shall discuss different possible arrangements of particles resulting in several types of structures. The correlation between the nature of interactions within the constituent particles and several properties of solids will also be explored. How these properties get modified due to the structural imperfections or by the presence of impurities in minute amounts would also be discussed.
General Characteristics of Solid State
In Class XI you have learnt that matter can exist in three states namely, solid, liquid and gas. Under a given set of conditions of temperature and pressure, which of these would be the most stable state of a given substance depends upon the net effect of two opposing factors. Intermolecular forces tend to keep the molecules (or atoms or ions) closer, whereas thermal energy tends to keep them apart by making them move faster. At sufficiently low temperature, the thermal energy is low and intermolecular forces bring them so close that they cling to one another and occupy fixed positions. These can still oscillate about their mean positions and the substance exists in solid state.
INTRODUCTION TO SOLID STATE
The following are the characteristic properties of the solid state:
(i) They have definite mass, volume and shape.
(ii) Intermolecular distances are short.
(iii) Intermolecular forces are strong.
(iv) Their constituent particles (atoms, molecules or ions) have fixed
positions and can only oscillate about their mean positions.
(v) They are incompressible and rigid.
AMORPHOUS AND CRYSTALLINE SOLIDS
Solids can be classified as crystalline or amorphous on the basis of the nature of order present in the arrangement of their constituent particles. A crystalline solid usually consists of a large number of small crystals, each of them having a definite characteristic geometrical shape. In a crystal, the arrangement of constituent particles (atoms, molecules or ions) is ordered. It has long range order which means that there is a regular pattern of arrangement of particles which repeats itself periodically over the entire crystal. Sodium chloride and quartz are typical examples of crystalline solids. An amorphous solid (Greek amorphos = no form) consists of particles of irregular shape. The arrangement of constituent particles (atoms, molecules or ions) in such a solid has only short range order. In such an arrangement, a regular and periodically repeating pattern is observed over short distances only. Such portions are scattered and in between the arrangement is disordered. The structures of quartz (crystalline) and quartz glass (amorphous) are shown in Fig. (a) and (b) respectively. While the two structures are almost identical, yet in the case of amorphous quartz glass there is no long range order. The structure of amorphous solids is similar to that of liquids. Glass, rubber and plastics are typical examples of amorphous solids. Due to the differences in the arrangement of the constituent particles, the two types of solids differ in their properties.
Two dimensional structure of (a) quartz and (b) quartz glass
Crystalline solids have a sharp melting point. On the other hand, amorphous solids soften over a range of temperature and can be moulded and blown into various shapes. On heating they become crystalline at some temperature.
Anisotropy in crystals is due to different arrangement of particles along different directions.
Some glass objects from ancient civilisations are found to become milky in appearance because of some crystallisation. Like liquids, amorphous solids have a tendency to flow, though very slowly. Therefore, sometimes these are called pseudo solids or super cooled liquids. Glass panes fixed to windows or doors of old buildings are invariably found to be slightly thicker at the bottom than at the top. This is because the glass flows down very slowly and makes the bottom portion slightly thicker. Crystalline solids are anisotropic in nature, that is, some of their physical properties like electrical resistance or refractive index show different values when measured along different directions in the same crystals. This arises from different arrangement of particles in different directions. This is illustrated in Fig. Since the arrangement of particles is different along different directions, the value of same physical property is found to be different along each direction. Amorphous solids on the other hand are isotropic in nature. It is because there is no long range order in them and arrangement is irregular along all the directions. Therefore, value of any physical property would be same along any direction. These differences are summarised in Table
Distinction between Crystalline and Amorphous Solids
| Property | Crystalline solids | Amorphous solids |
| Shape | Definite characteristic geometrical shape | Irregular shape |
| Melting point | Melt at a sharp and characteristic temperature |
Gradually soften over a range of temperature |
| Cleavage property |
When cut with a sharp edged tool, they split into two pieces and the newly generated surfaces are plain and smooth |
When cut with a sharp edged tool, they cut into two pieces with irregular surfaces |
| Heat of fusion | They have a definite and characteristic heat of fusion |
They do not have definite heat of fusion |
| Anisotropy | Anisotropic in nature | Isotropic in nature |
| Nature | True solids | Pseudo solids or super cooled liquids |
| Order in arrangement of constituent particles |
Long range order | Only short range order. |
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.
Classification of Crystalline Solids
In Section, we have learnt about amorphous substances and that they have only short range order. However, most of the solid substances are crystalline in nature. For example, all the metallic elements like iron, copper and silver; non – metallic elements like sulphur, phosphorus and iodine and compounds like sodium chloride, zinc sulphide and naphthalene form crystalline solids. Crystalline solids can be classified on the basis of nature of intermolecular forces operating in them into four categories viz., molecular, ionic, metallic and covalent solids. Let us now learn about these categories.
Molecular Solids
Molecules are the constituent particles of molecular solids. These are further sub divided into the following categories:
(i) Non polar Molecular Solids :
They comprise of either atoms, for example, argon and helium or the molecules formed by non polar covalent bonds
for example H2, Cl2 and I2. In these solids, the atoms or molecules are held by weak dispersion forces or London forces about which you have learnt in Class XI.
These solids are soft and non-conductors of electricity. They have low melting points and are usually in liquid or gaseous state at room temperature and pressure.
(ii) Polar Molecular Solids :
The molecules of substances like HCl, SO2, etc. are formed by polar covalent bonds.
The molecules in such solids are held together by relatively stronger dipole-dipole interactions. These solids are soft and non-conductors of electricity.
Their melting points are higher than those of non polar molecular solids yet most of these are gases or liquids under room temperature and pressure.
Solid SO2 and solid NH3 are some examples of such solids.
(iii) Hydrogen Bonded Molecular Solids :
The molecules of such solids contain polar covalent bonds between H and F, O or N atoms. Strong hydrogen bonding binds molecules of such solids like H2O (ice). They are non-conductors of electricity. Generally they are volatile liquids or soft solids under room temperature and pressure.
Ionic Solids
Ions are the constituent particles of ionic solids. Such solids are formed by the three dimensional arrangements of cations and anionsbound by strong coulombic (electrostatic) forces. These solids are hard and brittle in nature. They have high melting and boiling points. Since the ions are not free to move about, they are electrical insulators in the solid state. However, in the molten state or when dissolved in water, the ions become free to move about and they conduct electricity.
Metallic Solids
Metals are orderly collection of positive ions surrounded by and held together by a sea of free electrons.These electrons are mobile and are evenly spread out throughout the crystal. Each metal atom contributes one or more electrons towards this sea of mobile electrons. These free and mobile electrons are responsible for high electrical and thermal conductivity of metals. When an electric field is applied, these electrons flow through the network of positive ions. Similarly, when heat is supplied to one portion of a metal, the thermal energy is uniformly spread throughout by free electrons. Another important characteristic of metals is their lustre and colour in certain cases. This is also due to the presence of free electrons in them. Metals are highly malleable and ductile.
Covalent or Network Solids
A wide variety of crystalline solids of non-metals result from the formation of covalent bonds between adjacent atoms throughout the crystal. They are also called giant molecules. Covalent bonds are strong and directional in nature, therefore atoms are held very strongly at their positions. Such solids are very hard and brittle. They have extremely high melting points and may even decompose before melting. They are insulators and do not conduct electricity. Diamond and silicon carbide are typical examples of such solids. Graphite is soft and a conductor of electricity. Its exceptional properties are due to its typical structure . Carbon atoms are arranged in different layers and each atom is covalently bonded to three of its neighbouring atoms in the same layer. The fourth valence electron of each atom is present between different layers and is free to move about. These free electrons make graphite a good conductor of electricity. Different layers can slide one over the other. This makes graphite a soft solid and a good solid lubricant.