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, and biodegradable polymers for packaging, bio-compliant solids for surgical implants, etc.
From our earlier studies, we know that liquids and gases are called 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
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. The following are the characteristic properties of the solid state:
- They have definite mass, volume and shape.
- Intermolecular distances are short.
- Intermolecular forces are strong.
- Their constituent particles (atoms, molecules or ions) have fixed positions and can only oscillate about their mean positions.
- 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.
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.
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. Some glass objects from ancient civilizations are found to become milky in appearance because of some crystallization. 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. 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.
Distinction between Crystalline and Amorphous Solids
- Definite characteristic geometrical shape
- Melt at a sharp and characteristic temperature
- When cut with a sharp edged tool, they split into two pieces and the newly generated surfaces are plain and smooth
- They have a definite and characteristic heat of fusion
- Anisotropic in nature
- True solids
- Long range order
- Irregular shape
- Gradually soften over a range of temperature
- When cut with a sharp edged tool, they cut into two pieces with irregular surfaces
- They do not have definite heat of fusion
- Isotropic in nature
- Pseudo solids or super cooled liquids
- 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
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.
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.
Ions are the constituent particles of ionic solids. Such solids are formed by the three dimensional arrangements of cations and anions bound 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.
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 luster and color 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
Wide variety of crystalline solids of non-metals results 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.